WO2017094871A1

WO2017094871A1 - Process release film, use thereof, and method of producing resin-sealed semiconductor using same

Info

Publication number: WO2017094871A1
Application number: PCT/JP2016/085859
Authority: WO
Inventors: 清水　勝; 健二志摩
Original assignee: 三井化学東セロ株式会社
Priority date: 2015-12-03
Filing date: 2016-12-02
Publication date: 2017-06-08
Also published as: KR20180072716A; CN108349122B; KR102172867B1; CN108349122A

Abstract

Provided is a process release film that, regardless of the mold structure and amount of release agent, enables facile release of a molded article after resin sealing, and that can produce a molded article free of appearance defects such as wrinkles and chipping. This problem is solved by a process release film that is a laminate film containing a release layer A, a heat-resistant resin layer B, and as desired a release layer A', wherein the contact angle between water and the release layer A (and release layer A' when present) is 90° to 130° and the laminate film has a prescribed thermal dimensional variation ratio and/or tensile elastic modulus, or is solved by a process release film that is a laminate film containing a release layer A, a heat-resistant resin layer B, and as desired a release layer A', wherein the contact angle between water and the release layer A (and release layer A' when present) of the laminate film is 90° to 130°, the surface resistivity value of the release layer A is not more than 1 x 10¹³ ohm/square, the heat-resistant resin layer B contains a layer B1 that contains a polymeric antistatic agent, and the laminate film has a prescribed thermal dimensional variation ratio and/or tensile elastic modulus.

Description

Release film for process, use thereof, and method for producing resin-encapsulated semiconductor using the same

The first and second inventions of the present application relate to a release film for a process, preferably a release film for a semiconductor sealing process, and in particular, when a semiconductor chip is placed in a mold and a resin is injected and molded, the semiconductor chip It is related with the mold release film for processes arrange | positioned between etc. and a metal mold | die inner surface, and the manufacturing method of a resin sealing semiconductor using the same.
The third and fourth inventions of the present application relate to a mold release film for a process, preferably a mold release film for a semiconductor sealing process, which can effectively suppress an appearance defect of a molded product, particularly an appearance defect due to wrinkles, and particularly in a mold. The present invention relates to a process release film disposed between a semiconductor chip or the like and an inner surface of a mold when a semiconductor chip or the like is placed and a resin is injection-molded, and a resin-encapsulated semiconductor manufacturing method using the same.

In recent years, with the reduction in size and weight of semiconductor packages and the like, it has been studied to reduce the amount of sealing resin used. And even if it reduces the usage-amount of sealing resin, in order to be able to adhere | attach the interface of a semiconductor chip etc. and resin firmly, reducing the quantity of the mold release agent contained in sealing resin is desired. . For this reason, as a method for obtaining the releasability between the sealing resin and the mold after the curing molding, a method in which a release film is disposed between the inner surface of the mold and the semiconductor chip or the like is employed.

As such a release film, a fluorine-based resin film (for example, Patent Documents 1 and 2), a poly-4-methyl-1-pentene resin film (for example, Patent Document 3), etc., which are excellent in releasability and heat resistance. Proposed. However, these release films have a problem that wrinkles are easily generated when they are mounted on the inner surface of the mold, and the wrinkles are transferred to the surface of the molded product, resulting in poor appearance.

On the other hand, a laminated release film having a release layer and a heat-resistant layer has been proposed. These release films are intended to obtain releasability with a release layer and to suppress wrinkles and appearance defects with a heat-resistant layer. A representative one of these proposals pays attention to the relationship between the storage elastic modulus of the release layer and the heat-resistant layer (see, for example, Patent Documents 4 to 6). For example, Patent Document 4 discloses a laminated release film having a configuration in which the storage elastic modulus of the release layer is relatively low and the storage elastic modulus of the heat-resistant layer is relatively high, more specifically, the release layer at 175 ° C. A release film for a semiconductor encapsulation process is described in which the storage elastic modulus E ′ is 45 MPa or more and 105 MPa or less, and the storage elastic modulus E ′ of the heat resistant layer at 175 ° C. is 100 MPa or more and 250 MPa or less.
Such a release film for a process can be used not only in a semiconductor sealing process but also in a molding process of a reflector for a light emitting element such as a light emitting diode (see, for example, Patent Document 7).

In addition, charging of the release film also causes a poor appearance of the molded product. Since the release film used in the semiconductor sealing process is a resin film as described above, it is generally easily charged. For example, when unwinding and using a release film, static electricity is generated when the release film is peeled off, and foreign matter such as dust existing in the manufacturing atmosphere adheres to the charged release film, resulting in abnormal shape of the molded product (foreign matter Such as adhesion) and mold contamination. In particular, some semiconductor chip sealing devices employ a granular resin as a sealing resin, resulting in abnormal shapes and mold contamination due to the dust generated from the granular resin adhering to the release film. Appearance defects that cannot be ignored.
In recent years, an increase in the number of packages in which a semiconductor chip is flip-chip bonded and the back surface of the chip is exposed due to the demand for thinner packages and improved heat dissipation. This process is called a Molded Under Film (MUF) process. In the MUF process, sealing is performed in a state where the release film and the semiconductor chip are in direct contact with each other in order to protect and mask the semiconductor chip. At this time, if the release film is easily charged, there is a concern that the semiconductor chip is destroyed by charge-discharge at the time of peeling.
For this reason, various techniques for preventing the sealing film from being charged have been proposed. For example, Patent Document 6 discloses a first thermoplastic resin layer that contacts a curable resin at the time of formation, a second thermoplastic resin layer that contacts a mold, a first thermoplastic resin layer, and a second thermoplastic resin. There is described a release film comprising an intermediate layer disposed between the resin layer and the intermediate layer including a layer containing a polymer antistatic agent.

JP 2001-310336 A JP 2002-110722 A JP 2002-361443 A JP 2010-208104 A International Publication No. 2015/133631 A1 Pamphlet International Publication No. 2015/133630 A1 Pamphlet JP 2014-14928 A

However, with the development of this technical field, the level of requirements for process release films such as semiconductor encapsulation process release films has been increasing year by year, and process release with reduced generation of wrinkles even under more severe process conditions. There is a need for mold films, and in particular, there is a strong demand for process release films that balance mold release, suppression of wrinkles, and mold followability at a higher level.
Furthermore, there is a demand for a release film for a process in which the appearance defect of a molded product is suppressed even under more severe process conditions. In particular, the mold release property, the appearance defect suppression, and the mold followability are extremely high. In particular, there is a strong demand for process release films that are balanced at a high level.

The first invention of the present application was made in view of such circumstances, and the molded product after resin sealing can be easily released without depending on the mold structure or the amount of the release agent, and wrinkles, chips, etc. An object of the present invention is to provide a release film for a process capable of obtaining a molded product having no poor appearance.
The second invention of the present application was made in view of such circumstances, and the molded product after resin sealing can be easily released without using a mold structure or a release agent, and has wrinkles, chips or shapes. Separation for process that can obtain molded products with no appearance defects such as abnormalities (for example, burr generated due to static electricity adhesion to release film of granular sealing resin at normal temperature, adhesion of foreign matter, etc.) An object is to provide a mold film.
The third invention of the present application was made in view of such circumstances, and the molded product after resin sealing can be easily released without depending on the mold structure or the amount of the release agent, and wrinkles, chips, etc. An object of the present invention is to provide a release film for a process capable of obtaining a molded product having no poor appearance.
The fourth invention of the present application has been made in view of such circumstances, and can easily release a molded product after resin sealing without using a mold structure or a release agent, and has a wrinkle, a chip, or a shape. An object of the present invention is to provide a release film for a process capable of obtaining a molded product having no appearance defects such as abnormalities (such as adhesion of foreign matter).

As a result of intensive studies to solve the above problems, the present inventors have determined that the rate of thermal dimensional change at a specific temperature of the process release film, particularly the TD direction of the laminated film constituting the process release film (film Is a direction perpendicular to the longitudinal direction when the film is manufactured (hereinafter also referred to as “lateral direction”). The present invention has been found to be important for the suppression of wrinkles, and the present invention has been completed.
Furthermore, as a result of intensive studies to solve the above problems, the present inventors have determined that the rate of thermal dimensional change at a specific temperature of the process release film, particularly the TD direction of the laminated film constituting the process release film. We found that it is important to control the rate of thermal dimensional change and to provide a layer containing a polymer-based charging agent in the heat-resistant resin layer constituting the laminated film in order to suppress the appearance defect. 2 The invention has been completed.
In addition, as a result of intensive studies to solve the above problems, the present inventors have determined that the rate of thermal dimensional change at a specific temperature of the process release film, particularly the TD direction of the laminated film constituting the process release film ( In the plane of the film, the direction perpendicular to the longitudinal direction during film production (hereinafter also referred to as the “lateral direction”) is appropriately mounted on the inner surface of the mold. The present invention has been found to be important for the suppression of wrinkles, and the third invention of the present application has been completed.
In addition, the present inventors have made extensive studies to solve the above problems, and as a result, appropriately controlled the tensile elastic modulus at a specific temperature of the process release film, and constitutes the laminated film. In addition, the present inventors have found that it is particularly important to provide a layer containing a polymer-based charging agent in order to suppress poor appearance, and have completed the fourth invention of the present application.
That is, the first invention of the present application and each aspect thereof are as described in the following [1] to [19].

[1]
A release film for process that is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with water (hereinafter, “contact angle with water” may be referred to as “water contact angle”) is 90 ° to 130 °,
The release film for a process as described above, wherein the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 1B is 3% or less.
[2]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less, [1 ] The release film for processes as described in any one of Claims 1-3.
[3]
A release film for process which is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 1B is 4% or less.
[4]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the laminated film is 7% or less, [3 ] The release film for processes as described in any one of Claims 1-3.
[5]
The process release film according to any one of [1] to [4], wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less.
[6]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 1B is 6% or less. [5] The release film for a process according to [5].
[7]
The process release film according to any one of [1] to [4], wherein a rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less.
[8]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 1B is 4% or less. [7] The process release film according to [7].
[9]
In any one of [1] to [8], the release layer 1A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. The release film for process as described.
[10]
The process release film according to any one of [1] to [9], wherein the heat-resistant resin layer 1B includes a stretched film.
[11]
The release film for process according to [10], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
[12]
[1] to [11], wherein the heat amount of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat-resistant resin layer 1B is 15 J / g or more and 60 J / g or less. The release film for processes as described in any one of these.

[13]
The laminated film further has a release layer 1A ′, and includes the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ in this order,
The release film for a process according to any one of [1] to [12], wherein a contact angle of the release layer 1A ′ with respect to water is 90 ° to 130 °.
[14]
At least one of the release layer 1A and the release layer 1A ′ contains a resin selected from the group consisting of a fluororesin, 4-methyl-1-pentene (co) polymer, and polystyrene resin [13] Release film for process as described in 2.
[15]
The process release film [16] according to any one of [1] to [14], which is used for a sealing process with a thermosetting resin.
The process release film according to any one of [1] to [15], which is used in a semiconductor sealing process.
[17]
The release film for a process according to any one of [1] to [15], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
[18]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for a semiconductor sealing process according to any one of [1] to [14] on the inner surface of the molding die so that the release layer 1A faces the semiconductor device; ,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
[19]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing the release film for semiconductor sealing process according to [13] or [14] on the inner surface of the molding die so that the release layer 1A ′ faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:

Further, the second invention of the present application and each aspect thereof are as described in the following [20] to [40].

[20]
A release film for process which is a laminated film including a release layer 2A and a heat resistant resin layer 2B,
The contact angle of the release film 2A of the laminated film with respect to water is 90 ° to 130 °, and the surface specific resistance value is 1 × 10 ¹³ Ω / □ or less,
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
[21]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less, [20 ] The release film for processes as described in any one of Claims 1-3.
[22]
A release film for process which is a laminated film including a release layer 2A and a heat resistant resin layer 2B,
The contact angle of the release film 2A of the laminated film with respect to water is 90 ° to 130 °, and the surface specific resistance value is 1 × 10 ¹³ Ω / □ or less,
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
[23]
The sum of the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the laminated film is 7% or less, [22 ] The release film for processes as described in any one of Claims 1-3.
[24]
The process according to any one of [20] to [23], wherein the heat-resistant resin layer 2B includes a layer 2B1 containing a polymeric antistatic agent and an adhesive layer 2B2 containing an adhesive. Release film.
[25]
Process release film according to any one of [20] to [24], wherein a rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 2B is 3% or less. .
[26]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 2B is 6% or less. [25] The release film for a process according to [25].
[27]
Process release film according to any one of [20] to [24], wherein a rate of thermal dimensional change from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 2B is 3% or less. .
[28]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 2B is 4% or less. [27] The release film for a process according to [27].
[29]
Any one of [20] to [28], wherein the release layer 2A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. The release film for process as described.
[30]
The process release film according to any one of [20] to [29], wherein the heat resistant resin layer 2B includes a stretched film.
[31]
The process release film according to [30], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
[32]
From [20] to [31], the heat of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat-resistant resin layer 2B is 15 J / g or more and 60 J / g or less. The release film for a process as described in any one of Claims.
[33]
The laminated film further has a release layer 2A ′, and includes the release layer 2A, the heat-resistant resin layer 2B, and the release layer 2A ′ in this order,
The release film for process according to any one of [20] to [32], wherein a contact angle of the release layer 2A ′ with water is 90 ° to 130 °.
[34]
The release film for process according to [33], wherein the release layer 2A ′ has a surface specific resistance value of 1 × 10 ¹³ Ω / □ or less.
[35]
At least one of the release layer 2A and the release layer 2A ′ includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin [14] Or the release film for processes as described in [15].
[36]
The process release film [37] according to any one of [20] to [35], which is used for a sealing process with a thermosetting resin.
The process release film according to any one of [20] to [36], which is used in a semiconductor sealing process.
[38]
The release film for a process according to any one of [20] to [36], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
[39]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for semiconductor sealing process according to any one of [20] to [35] on the inner surface of the molding die so that the release layer 2A faces the semiconductor device; ,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
[40]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
The step of disposing the release film for semiconductor sealing process according to any one of [33] to [35] on the inner surface of the molding die so that the release layer 2A ′ faces the semiconductor device. When,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:

Further, the third invention of the present application and each aspect thereof are as described in [41] to [61] below.

[41]
A release film for process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
[42]
The mold release film for a process according to [41], wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
[43]
The sum of the rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction and the rate of thermal dimensional change from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less, [41 ] Or a release film for process according to [42].
[44]
A release film for process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
[45]
The mold release film for a process according to [44], wherein a rate of thermal dimensional change from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
[46]
The sum of the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the laminated film is 7% or less, [44 ] Or a release film for process according to [45].
[47]
Process release film according to any one of [41] to [46], wherein the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less. .
[48]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 3B is 6% or less. [47] The release film for a process according to [47].
[49]
The process release film according to any one of [41] to [46], wherein a thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less. .
[50]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 3B is 5% or less. [49] The release film for a process according to [49].
[51]
Any one of [41] to [50], wherein the release layer 3A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. The release film for process as described.
[52]
The process release film according to any one of [41] to [51], wherein the heat resistant resin layer 3B includes a stretched film.
[53]
The release film for process according to [52], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
[54]
Any of [41] to 53], wherein the heat of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat resistant resin layer 3B is 20 J / g or more and 100 J / g or less. A release film for a process according to claim 1.
[55]
The laminated film further has a release layer 3A ′, and includes the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ in this order,
The release film for process according to any one of [41] to [54], wherein a contact angle of the release layer 3A 'with water is 90 ° to 130 °.
[56]
At least one of the release layer 3A and the release layer 3A ′ includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin [55] Release film for process as described in 2.
[57]
The process release film [58] according to any one of [41] to [56], which is used for a sealing process with a thermosetting resin.
The process release film according to any one of [41] to [57], which is used in a semiconductor sealing process.
[59]
The release film for a process according to any one of [41] to [57], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
[60]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for semiconductor sealing process according to any one of [41] to [56] on the inner surface of the molding die so that the release layer 3A faces the semiconductor device; ,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
[61]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for semiconductor sealing process according to [55] or [56] on the inner surface of the molding die so that the release layer 3A ′ faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:

Further, the fourth invention of the present application and each aspect thereof are as described in the following [62] to [86].

[62]
A release film for process which is a laminated film including a release layer 4A and a heat resistant resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
[63]
The mold release film for a process according to [62], wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
[64]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less, ] Or a process release film according to [63].
[65]
A release film for process which is a laminated film including a release layer 4A and a heat resistant resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
[66]
The mold release film for process according to [65], wherein a rate of thermal dimensional change from 23 ° C to 170 ° C in the transverse (TD) direction of the laminated film is 4% or less.
[67]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the laminated film is 7% or less, ] Or a process release film according to [66].
[68]
The process according to any one of [62] to [67], wherein the heat resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent and an adhesive layer 4B2 containing an adhesive. Release film.
[69]
The process release film according to any one of [62] to [67], wherein the heat-resistant resin layer 4B includes a layer 4B3 containing a polymeric antistatic agent and an adhesive.
[70]
The process release film according to any one of [62] to [69], wherein a thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction of the heat-resistant resin layer 4B is 3% or less. .
[71]
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 4B is 6% or less. [70] The release film for a process according to [70].
[72]
Process release film according to any one of [62] to [69], wherein a rate of thermal dimensional change from 23 ° C to 170 ° C in the transverse (TD) direction of the heat-resistant resin layer 4B is 3% or less. .
[73]
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 4B is 5% or less. [72] The release film for a process according to [72].
[74]
In any one of [62] to [73], the release layer 4A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. The release film for process as described.
[75]
The mold release film for a process according to any one of [62] to [74], wherein the heat resistant resin layer 4B comprises a stretched film.
[76]
The process release film according to [75], wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
[77]
From [62] to [76], the heat of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat resistant resin layer 4B is 20 J / g or more and 100 J / g or less. The release film for a process as described in any one of Claims.
[78]
The process release film according to any one of [62] to [77], wherein the surface specific resistance value of the release layer 4A is 1 × 10 ¹³ Ω / □ or less.
[79]
The laminated film further has a release layer 4A ′, and includes the release layer 4A, the heat-resistant resin layer 4B, and the release layer 4A ′ in this order,
The release film for process according to any one of [62] to [78], wherein a contact angle of the release layer 4A ′ with respect to water is 90 ° to 130 °.
[80]
At least one of the release layer 4A and the release layer 4A ′ contains a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin [79] Release film for process as described in 2.
[81]
The release film for process according to [79] or [80], wherein the surface specific resistance value of the release layer 4A ′ is 1 × 10 ¹³ Ω / □ or less.
[82]
The process release film [83] according to any one of [62] to [81], which is used for a sealing process with a thermosetting resin.
The process release film according to any one of [62] to [82], which is used in a semiconductor sealing process.
[84]
The release film for process according to any one of [62] to [82], which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
[85]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for semiconductor encapsulation process according to any one of [62] to [83] on the inner surface of the molding die so that the release layer 4A faces the semiconductor device; ,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
[86]
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing the release film for semiconductor sealing process according to any one of [79] to [81] on the inner surface of the molding die so that the release layer 4A ′ faces the semiconductor device. When,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
In the present application, the “semiconductor device” is a concept including a semiconductor element (chip).

The process release film of the first invention of the present application has a high level of releasability, suppression of wrinkles, and mold followability that could not be realized by the prior art. A molded product obtained by sealing or the like can be easily released, and a molded product free from appearance defects such as wrinkles and chips can be manufactured with high productivity.
The process release film of the second invention of the present application has a high level of mold release property, suppression of appearance defects, and mold followability that could not be realized by the prior art. A molded product obtained by resin sealing or the like can be easily released, and a molded product free from defects in appearance such as wrinkles, chips, and abnormal shapes (such as adhesion of foreign matter) can be produced with high productivity. Furthermore, even if the sealing resin is a solid granule at room temperature, molding defects such as burrs caused by the adhesion of the sealing resin to the release film due to static electricity can be suppressed in advance. The process release film of the second invention of the present application is particularly suitable for use in a sealing apparatus that employs a granular resin as the sealing resin.
The process release film of the third invention of the present application has a high level of releasability, suppression of wrinkles, and mold followability that could not be realized by the prior art. A molded product obtained by sealing or the like can be easily released, and a molded product free from appearance defects such as wrinkles and chips can be manufactured with high productivity.
The process release film of the fourth invention of the present application has a high level of mold release property, suppression of appearance defects, and mold followability that could not be realized by the prior art. A molded product obtained by resin sealing or the like can be easily released, and a molded product free from defects in appearance such as wrinkles, chips, and abnormal shapes (such as adhesion of foreign matter) can be produced with high productivity. The process release film of the fourth invention of the present application is particularly suitable for use in a sealing device that employs a granular resin as the sealing resin.

It is a schematic diagram which shows an example of the mold release film for processes of this invention. It is a schematic diagram which shows the other example of the release film for processes of this invention. It is a schematic diagram which shows an example of the manufacturing method of the resin sealing semiconductor using the release film for processes of this invention 1st invention, 3rd invention, and 4th invention. It is a schematic diagram which shows an example of the manufacturing method of the resin sealing semiconductor using the mold release film for a process of this-application 2nd invention. It is a schematic diagram which shows an example of the manufacturing method of the resin sealing semiconductor using the mold release film for processes of this invention. It is a schematic diagram which shows an example of the manufacturing method of the resin sealing semiconductor using the mold release film for processes of this invention. It is a schematic diagram which shows an example of the resin sealing semiconductor obtained with the manufacturing method of the resin sealing semiconductor of FIG. 4A and 4B.

Process Release Film The process release film of the first invention of the present application includes the following four aspects.
(1-1)
A release film for process that is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
(1-2)
A release film for process that is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
(1st-3 aspects)
A release film for process which is a laminated film including the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ in this order,
The contact angle of the release layer 1A and the release layer 1A ′ with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
(1st to 4th aspects)
A release film for process which is a laminated film including the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ in this order,
The contact angle of the release layer 1A and the release layer 1A ′ with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.

As is clear from the above embodiments, the process release film of the first invention of the present application (hereinafter, also simply referred to as “release film”) has a release layer 1A having release properties for molded products and molds, and A laminated film including a release layer 1A ′ and a heat-resistant resin layer 1B that supports the release layer as desired.

The process release film of the first invention of the present application is disposed on the inner surface of a molding die when a semiconductor element or the like is resin-sealed inside the molding die. At this time, the release layer 1A of the release film (may be the release layer 1A ′ when the release layer 1A ′ is present) is placed on the resin-encapsulated semiconductor element or the like (molded product) side. It is preferable to arrange. By disposing the release film of the first invention of the present application, the resin-encapsulated semiconductor element and the like can be easily released from the mold.
The contact angle of the release layer 1A with respect to water is 90 ° to 130 °. By having such a contact angle, the release layer 1A has low wettability and is fixed to the cured sealing resin or the mold surface. Without this, the molded product can be easily released.
The contact angle of the release layer 1A with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.

As described above, the release layer 1A (in some cases, the release layer 1A ′) is disposed on the molded product side, so that the mold in the release layer 1A (in some cases, the release layer 1A ′) in the resin sealing step. It is preferable to suppress the occurrence of. This is because the generated wrinkles are transferred to the molded product and the appearance defect of the molded product is highly likely to occur.

In the first invention of the present application, in order to achieve the above-mentioned object, as the laminated film constituting the process release film, the release layer 1A (and the release layer 1A ′ if necessary) and the release layer are supported. A laminated film including the heat-resistant resin layer 1 B, in which a thermal dimensional change rate in the transverse (TD) direction shows a specific value is used.
That is, the laminated film including the release layer 1A (and the release layer 1A ′ if necessary) and the heat-resistant resin layer 1B that supports the release layer is from 23 ° C. to 120 ° C. in the TD direction (lateral direction). The rate of thermal dimensional change in the TD direction (lateral direction) from 23 ° C. to 170 ° C. is 4% or less. Further, the laminated film has a thermal dimensional change rate of 23% to 120 ° C. in the TD direction (lateral direction) of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The rate is more preferably 4% or less.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). When the rate is 4% or less, generation of wrinkles in the release layer in the resin sealing step or the like can be effectively suppressed. The mechanism that suppresses the occurrence of wrinkles in the release layer is not always clear by using a film having a specific rate of thermal dimensional change in the transverse (TD) direction as a laminated film constituting the release film for the process. However, there is a relation with the fact that the thermal expansion / shrinkage of the release layer 1A (or the release layer 1A ′) due to heating / cooling during the process is suppressed by using a laminated film having relatively small thermal expansion / shrinkage. Presumed to be.

The laminated film constituting the process release film of the first invention of the present application preferably has a thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of 2.5% or less. It is more preferably 0% or less, and further preferably 1.5% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate of −5.0% or more from 23 ° C. to 120 ° C. in the TD direction (lateral direction).
2. The laminated film constituting the process release film of the first invention of the present application preferably has a thermal dimensional change rate of 23% to 170 ° C. in the TD direction (lateral direction) of 3.5% or less. It is more preferably 0% or less, and further preferably 2.0% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate of −5.0% or more from 23 ° C. to 170 ° C. in the TD direction (lateral direction).

The mechanism by which the generation of wrinkles in the release layer is more effectively suppressed by using a resin layer in which the rate of thermal dimensional change in the transverse (TD) direction exhibits the specific value as the heat resistant resin layer 1B is not necessarily clear. However, the thermal expansion / contraction of the release layer 1A (or the release layer 1A ′) due to heating / cooling during the process is suppressed by using the heat-resistant resin layer 1B having relatively small thermal expansion / contraction. It is presumed to be related.

The process release film of the first invention of the present application, which is a laminated film including the release layer 1A (and the release layer 1A ′ if necessary) and the heat-resistant resin layer 1B that supports the release layer, has a TD direction ( It is preferable that the sum of the thermal dimensional change rate in the transverse direction and the thermal dimensional change rate in the MD direction (longitudinal direction during production of the film; hereinafter referred to as “longitudinal direction”) is not more than a specific value.
That is, the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less. On the other hand, the laminated film is the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the vertical (MD) direction. Is preferably −5.0% or more.
Thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and longitudinal (MD) direction of the laminated film including the release layer 1A (and the release layer 1A ′ if necessary) and the heat-resistant resin layer 1B. When the sum of the thermal dimensional change rates from 23 ° C. to 120 ° C. is 6% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.

Further, the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and longitudinal (MD) of the laminated film including the release layer 1A (and release layer 1A ′ if necessary) and the heat-resistant resin layer 1B. The sum of the thermal dimensional change rates from 23 ° C. to 170 ° C. in the direction is preferably 7% or less, while the laminated film has a thermal dimension from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The sum of the rate of change and the rate of change in the thermal dimension from 23 ° C. to 170 ° C. in the machine direction (MD) is preferably −5.0% or more.
By the sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction being 7% or less, Generation of wrinkles when mounted on the inner surface of the mold can be further effectively suppressed.

Release layer 1A
The release layer 1A constituting the process release film of the first invention of the present application has a contact angle with water of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115. °, more preferably 100 ° to 110 °. In view of excellent mold releasability and availability, it is preferable to include a resin selected from the group consisting of a fluororesin, 4-methyl-1-pentene (co) polymer, and a polystyrene resin.

The fluororesin that can be used for the release layer 1A may be a resin containing a structural unit derived from tetrafluoroethylene. Although it may be a homopolymer of tetrafluoroethylene, it may be a copolymer with other olefins. Examples of other olefins include ethylene. A copolymer containing tetrafluoroethylene and ethylene as monomer constitutional units is a preferred example. In such a copolymer, the proportion of constitutional units derived from tetrafluoroethylene is 55 to 100% by mass. The proportion of the structural unit derived from is preferably 0 to 45% by mass.

The 4-methyl-1-pentene (co) polymer that can be used for the release layer 1A may be a homopolymer of 4-methyl-1-pentene, and 4-methyl-1-pentene, It may be a copolymer with other olefins having 2 to 20 carbon atoms (hereinafter referred to as “olefins having 2 to 20 carbon atoms”).

In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, the olefin having 2 to 20 carbon atoms to be copolymerized with 4-methyl-1-pentene is 4-methyl It can give flexibility to -1-pentene. Examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, -Octadecene, 1-eicosene and the like are included. These olefins may be used alone or in combination of two or more.

In the case of a copolymer of 4-methyl-1-pentene and an olefin having 2 to 20 carbon atoms, the proportion of structural units derived from 4-methyl-1-pentene is 96 to 99% by mass; The proportion of the structural unit derived from the olefin having 2 to 20 carbon atoms is preferably 1 to 4% by mass. By reducing the content of structural units derived from olefins having 2 to 20 carbon atoms, the copolymer can be hardened, that is, the storage elastic modulus E ′ can be increased, and the generation of wrinkles in the sealing process and the like can be suppressed. Is advantageous. On the other hand, by increasing the content of structural units derived from olefins having 2 to 20 carbon atoms, the copolymer can be softened, that is, the storage elastic modulus E ′ can be lowered, and the mold followability can be improved. Is advantageous.

4-Methyl-1-pentene (co) polymer can be produced by methods known to those skilled in the art. For example, it can be produced by a method using a known catalyst such as a Ziegler-Natta catalyst or a metallocene catalyst. The 4-methyl-1-pentene (co) polymer is preferably a highly crystalline (co) polymer. The crystalline copolymer may be either a copolymer having an isotactic structure or a copolymer having a syndiotactic structure, but in particular a copolymer having an isotactic structure. Is preferable from the viewpoint of physical properties and is easily available. Furthermore, if 4-methyl-1-pentene (co) polymer can be formed into a film and has the strength to withstand the temperature and pressure during molding, the stereoregularity and molecular weight are also particularly limited. Not. The 4-methyl-1-pentene copolymer may be a commercially available copolymer such as TPX (registered trademark) manufactured by Mitsui Chemicals, Inc.

Polystyrene resins that can be used for the release layer 1A include styrene homopolymers and copolymers, and the structural unit derived from styrene contained in the polymer is at least 60% by weight or more. Preferably, it is 80% by weight or more.
The polystyrene resin may be isotactic polystyrene or syndiotactic polystyrene, but is preferably isotactic polystyrene from the viewpoint of transparency, availability, release properties, heat resistance, etc. From this point of view, syndiotactic polystyrene is preferable. Polystyrene may be used alone or in combination of two or more.

The release layer 1A preferably has heat resistance that can withstand the mold temperature during molding (typically 120 to 180 ° C.). From such a viewpoint, the release layer 1A preferably includes a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 190 ° C. or higher, and more preferably 200 ° C. or higher and 300 ° C. or lower.
In order to provide crystallinity to the release layer 1A, for example, a fluororesin preferably contains at least a structural unit derived from tetrafluoroethylene, and a 4-methyl-1-pentene (co) polymer has 4-methyl-1 -It preferably contains at least a structural unit derived from pentene, and in a polystyrene resin, it preferably contains at least syndiotactic polystyrene. By including a crystal component in the resin constituting the release layer 1A, it is difficult for wrinkles to occur in the resin sealing process and the like, and it is suitable for suppressing wrinkles from being transferred to a molded product to cause poor appearance. .

The resin containing the crystalline component constituting the release layer 1A has a heat of crystal melting of 15 J / g or more and 60 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221. It is preferable that it is 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, in addition to being able to more effectively express heat resistance and releasability that can withstand hot press molding in the resin sealing step, etc., it also suppresses the dimensional change rate. Therefore, generation of wrinkles can be prevented. On the other hand, if the heat of crystal fusion is 60 J / g or less, the release layer 1A has an appropriate hardness, so that sufficient followability to the mold of the film can be obtained in the resin sealing step or the like. There is no risk of film damage.

The release layer 1A may further contain other resins in addition to the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin. In this case, it is preferable that the hardness of the other resin is relatively high. Examples of other resins include polyamide-6, polyamide-66, polybutylene terephthalate, and polyethylene terephthalate. Thus, even when the release layer 1A contains a large amount of soft resin (for example, when the 4-methyl-1-pentene copolymer contains a large amount of olefins having 2 to 20 carbon atoms), the hardness of the release layer 1A is relatively high. By further including a high resin, the release layer 1A can be hardened, which is advantageous in suppressing wrinkles in the sealing process and the like.

The content of these other resins is preferably, for example, 3 to 30% by mass with respect to the resin component constituting the release layer 1A. By setting the content of other resins to 3 mass or more, the effect of addition can be made substantial, and by setting the content to 30 mass% or less, the releasability for a mold or a molded product is maintained. be able to.

In addition to the fluororesin, 4-methyl-1-pentene (co) polymer, and / or polystyrene resin, the release layer 1A includes a heat resistance stabilizer, weather resistance, and the like within a range not impairing the object of the first invention of the present application. You may also contain the well-known additive generally mix | blended with resin for films, such as a stabilizer, a rust prevention agent, a copper-resistant damage stabilizer, and an antistatic agent. The content of these additives can be, for example, 0.0001 to 10 parts by weight with respect to 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 1A is not particularly limited as long as the release property for the molded product is sufficient, but is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer 1A may have a concavo-convex shape as necessary, thereby improving the releasability. The method for imparting irregularities to the surface of the release layer 1A is not particularly limited, but a general method such as embossing can be employed.

Release layer 1A '
The process release film of the first invention of the present application may further have a release layer 1A ′ in addition to the release layer 1A and the heat-resistant resin layer 1B. That is, the process release film of the first invention of the present application may be a process release film that is a laminated film including the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ in this order. Good.
The contact angle with respect to water of the release layer 1A ′ that may constitute the process release film of the first invention of the present application is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98. It is from ° to 115 °, more preferably from 100 ° to 110 °. The preferable material, configuration, physical properties, and the like of the release layer 1A ′ are the same as those described above for the release layer 1A.

The release layer 1A and the release layer 1A ′ are the same when the release film for the process is a laminated film including the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ in this order. It may be a layer having a different structure or a layer having a different structure.
From the standpoints of warpage prevention and ease of handling due to the same releasability on both surfaces, the release layer 1A and the release layer 1A ′ may have the same or substantially the same configuration. Preferably, from the viewpoint of optimally designing each in relation to the process of using the release layer 1A and the release layer 1A ′, for example, the release layer 1A has excellent release properties from the mold. From the viewpoint of making the layer 1A ′ excellent in releasability from the molded product, it is preferable that the release layer 1A and the release layer 1A ′ have different configurations.
When the release layer 1A and the release layer 1A ′ have different configurations, the release layer 1A and the release layer 1A ′ may be made of the same material and have different configurations such as thickness. However, the materials and other configurations may be different.

Heat resistant resin layer 1B
The heat-resistant resin layer 1B constituting the process release film of the first invention of the present application has a function of supporting the release layer 1A (and possibly the release layer 1A ') and suppressing wrinkles due to mold temperature and the like. Have.
In the process release film of the first invention of this application, the rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less, or the heat-resistant resin layer 1B It is preferable that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the (TD) direction is 3% or less. Further, the heat resistant resin layer 1B has a thermal dimensional change rate of 23% to 120 ° C. in the transverse (TD) direction of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction. The rate is more preferably 3% or less.
Although any resin layer including an unstretched film can be used for the heat-resistant resin layer 1B, it is particularly preferable to comprise a stretched film.
The stretched film tends to have a low or negative coefficient of thermal expansion due to the influence of stretching in the manufacturing process, and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction is 3% or less. Alternatively, it is relatively easy to realize the characteristic that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 1B is 3% or less. It can be preferably used.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 1B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.
The thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 1B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.

The stretched film may be a uniaxially stretched film or a biaxially stretched film. In the case of a uniaxially stretched film, either longitudinal stretching or lateral stretching may be used, but it is desirable that stretching is performed at least in the transverse (TD) direction.
The method and apparatus for obtaining the stretched film are not particularly limited, and stretching may be performed by a method known in the art. For example, it can be stretched with a heating roll or a tenter stretching machine.

As the stretched film, a stretched film selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film is preferably used. These stretched films are relatively easy to reduce the thermal expansion coefficient in the transverse (TD) direction or to be negative by stretching, and the mechanical properties are suitable for the use of the first invention of the present application. In addition, since it is inexpensive and relatively easy to obtain, it is particularly suitable as a stretched film in the heat-resistant resin layer 1B.

As the stretched polyester film, a stretched polyethylene terephthalate (PET) film and a stretched polybutylene terephthalate (PBT) film are preferable, and a biaxially stretched polyethylene terephthalate (PET) film is particularly preferable.
There is no particular limitation on the polyamide constituting the stretched polyamide film, but polyamide-6, polyamide-66, etc. can be preferably used.
As the stretched polypropylene film, a uniaxially stretched polypropylene film, a biaxially stretched polypropylene film, or the like can be preferably used.
There is no particular limitation on the draw ratio, and the thermal dimensional change rate can be appropriately controlled, and an appropriate value may be set as appropriate in order to achieve suitable mechanical properties. For example, in the case of a stretched polyester film, the machine direction In the transverse direction, the range is preferably 2.7 to 8.0 times. In the case of a stretched polyamide film, the longitudinal direction and the transverse direction are preferably in the range of 2.7 to 5.0 times. In the case of a polypropylene film, in the case of a biaxially stretched polypropylene film, it is preferably in the range of 5.0 to 10.0 times in both the machine direction and the transverse direction. The range of 5 to 10.0 times is preferable.

The heat-resistant resin layer 1B has heat resistance that can withstand the mold temperature (typically 120 to 180 ° C.) at the time of molding from the viewpoint of controlling the strength of the film and the rate of thermal dimensional change within an appropriate range. It is preferable. From this point of view, the heat resistant resin layer 1B preferably includes a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 ° C. or higher, and the melting point is 155 ° C. or higher and 300 ° C. or lower. Is more preferably 185 to 210 ° C., and particularly preferably 185 to 205 ° C.

As described above, the heat-resistant resin layer 1B preferably contains a crystalline resin having a crystal component. As a crystalline resin to be contained in the heat resistant resin layer 1B, for example, a crystalline resin such as a polyester resin, a polyamide resin, or a polypropylene resin can be used for a part or all of the crystalline resin. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the crystalline resin in the heat-resistant resin layer 1B, it is more advantageous to suppress the occurrence of defects in the resin sealing process and the like, and to suppress the appearance of defects due to the transfer of defects to the molded product. Become.
The resin constituting the heat-resistant resin layer 1B preferably has a heat of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) in accordance with JISK7221 of 20 J / g or more and 100 J / g or less. It is more preferably 25 J / g or more and 65 J / g or less, more preferably 25 J / g or more and 55 J / g or less, more preferably 28 J / g or more and 50 J / g or less, and more preferably 28 J / g g or more and 40 J / g or less is more preferable, and 28 J / g or more and 35 J / g or less is more preferable. When it is 20 J / g or more, it is possible to effectively exhibit heat resistance and releasability that can withstand hot press molding in a resin sealing process and the like, and the dimensional change rate can be slightly suppressed. The occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal fusion is 100 J / g or less, the heat resistant resin layer 1B can be provided with an appropriate hardness, so that sufficient followability of the film to the mold is ensured in the resin sealing step and the like. In addition to being able to do so, there is no risk of the film being easily damaged. In the present embodiment, the crystal melting calorie is the calorific value (J / g) on the vertical axis obtained in the first heating step in the differential scanning calorimetry (DSC) measurement according to JISK7221 and the horizontal axis. In the chart showing the relationship with temperature (° C.), it is a numerical value obtained by the sum of peak areas having a peak at 120 ° C. or higher.
The amount of crystal melting heat of the heat-resistant resin layer 1B can be adjusted by appropriately setting the heating and cooling conditions and the stretching conditions during film production.

The thickness of the heat-resistant resin layer 1B is not particularly limited as long as the film strength can be secured, but is usually 1-1.
It is 00 μm, preferably 5 to 50 μm.

Other layers The release film for process of the first invention of the present application has layers other than the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ as long as the object of the first invention of the present application is not violated. May be. For example, an adhesive layer may be provided between the release layer 1A (or the release layer 1A ′) and the heat resistant resin layer 1B as necessary. The material used for the adhesive layer is not particularly limited as long as it can firmly bond the release layer 1A and the heat-resistant resin layer 1B and does not peel in the resin sealing step or the release step.

For example, when the release layer 1A (or release layer 1A ′) contains 4-methyl-1-pentene copolymer, the adhesive layer is modified 4-methyl-1 graft-modified with an unsaturated carboxylic acid or the like. It is preferably a pentene copolymer resin, an olefin adhesive resin composed of a 4-methyl-1-pentene copolymer and an α-olefin copolymer. When the release layer 1A (or the release layer 1A ') contains a fluororesin, the adhesive layer is preferably a pressure-sensitive adhesive such as polyester, acrylic or fluororubber. The thickness of the adhesive layer is not particularly limited as long as the adhesiveness between the release layer 1A (or the release layer 1A ') and the heat-resistant resin layer 1B can be improved, but it is, for example, 0.5 to 10 µm.

The total thickness of the process release film of the first invention of the present application is not particularly limited, but is preferably 10 to 300 μm, for example, and more preferably 30 to 150 μm. When the total thickness of the release film is in the above range, it is preferable because the handling property when used as a roll is good and the amount of discarded film is small.

Hereinafter, preferred embodiments of the process release film of the first invention of the present application will be described more specifically. FIG. 1 is a schematic diagram showing an example of a three-layer process release film. As shown in FIG. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one surface of the release film 16 with an adhesive layer 14 interposed therebetween.

The release layer 16 is the aforementioned release layer 1A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer 1B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing process; the heat-resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the mold in the sealing process.

FIG. 2 is a schematic diagram showing an example of a five-layer process release film. Members having the same functions as those in FIG. 1 are denoted by the same reference numerals. As shown in FIG. 2, the release film 20 includes a heat resistant resin layer 12 and a release layer 16 A and a release layer 16 B formed on both surfaces of the release film 16 via an adhesive layer 14. The release layer 16A is the aforementioned release layer 1A, the heat-resistant resin layer 12 is the aforementioned heat-resistant resin layer 1B, the release layer 16B is the aforementioned release layer 1A ', and the adhesive layer 14 is the aforementioned It is an adhesive layer.

The compositions of the release layers 16A and 16B may be the same as or different from each other. The thicknesses of the release layers 16A and 16B may be the same as or different from each other. However, it is preferable that the release layers 16A and 16B have the same composition and thickness as each other because a symmetric structure is obtained and the release film itself is hardly warped. In particular, since the release film of the first invention of the present application may be stressed by heating in the sealing process, it is preferable to suppress warping. As described above, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good release properties can be obtained on both the molded product and the inner surface of the mold.

Process Release Film Manufacturing Method The process release film of the first invention of the present application can be manufactured by any method. For example, 1) a method for producing a release film for a process by coextruding and laminating a release layer 1A and a heat resistant resin layer 1B (coextrusion forming method), and 2) on a film to be a heat resistant resin layer 1B In addition, the molten resin of the resin to be the release layer 1A and the adhesive layer is applied and dried, or the resin solution in which the resin to be the release layer 1A and the adhesive layer is dissolved in a solvent is applied and dried. Process for producing release film for process (coating method), 3) Production of a film to be the release layer 1A and a film to be the heat-resistant resin layer 1B in advance, and laminating these films Thus, there is a method for producing a release film for a process (lamination method).

In the method 3), as a method for laminating the resin films, various known laminating methods can be employed, and examples thereof include an extrusion laminating method, a dry laminating method, and a thermal laminating method.
In the dry laminating method, each resin film is laminated using an adhesive. As the adhesive, known adhesives for dry lamination can be used. For example, polyvinyl acetate adhesives; homopolymers or copolymers of acrylic esters (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or acrylic esters and other monomers (methacrylic acid) Polyacrylate adhesives consisting of copolymers with methyl, acrylonitrile, styrene, etc .; Cyanoacrylate adhesives; Ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid) Etc.) Ethylene copolymer adhesives made of copolymers, etc .; Cellulose adhesives; Polyester adhesives; Polyamide adhesives; Polyimide adhesives; Amino resin systems made of urea resins or melamine resins Adhesive; phenolic resin adhesive; epoxy adhesive; polyol (polyether polyol) , Polyester polyols, etc.) and isocyanate and / or isocyanurate crosslinkable polyurethane adhesives; reactive (meth) acrylic adhesives; rubber adhesives made of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc .; silicone Adhesives; inorganic adhesives made of alkali metal silicate, low melting point glass, etc .; other adhesives can be used. As the resin film laminated by the method 3), a commercially available one may be used, or one produced by a known production method may be used. The resin film may be subjected to surface treatment such as corona treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, and primer coating treatment. It does not specifically limit as a manufacturing method of a resin film, A well-known manufacturing method can be utilized.

1) The coextrusion molding method is preferable in that a defect due to a foreign matter biting between the resin layer to be the release layer 1A and the resin layer to be the heat-resistant resin layer 1B or a warp of the release film hardly occurs. . 3) The laminating method is a manufacturing method suitable when a stretched film is used for the heat resistant resin layer 1B. In this case, it is preferable to form an appropriate adhesive layer at the interface between the films as necessary. In order to improve the adhesiveness between the films, a surface treatment such as a corona discharge treatment may be applied to the interface between the films as necessary.

The process release film may be uniaxially or biaxially stretched as necessary, whereby the film strength of the film can be increased.

The coating means in the above 2) coating method is not particularly limited, but various coaters such as a roll coater, a die coater, and a spray coater are used. The melt extrusion means is not particularly limited. For example, an extruder having a T-type die or an inflation type die is used.

Manufacturing process The release film for a process of the first invention of the present application is used by placing a semiconductor chip or the like in a mold and injecting and molding a resin between the semiconductor chip and the inner surface of the mold. Can do. By using the process release film of the first invention of the present application, it is possible to effectively prevent mold release failure from the mold, generation of burrs, and the like.
The resin used in the manufacturing process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the technical field, and in particular, epoxy-based thermosetting resins are used. It is preferable to use it.
As the manufacturing process, semiconductor chip sealing is the most representative, but is not limited to this, and the first invention of the present application is also applicable to a fiber reinforced plastic molding process, a plastic lens molding process, and the like. Can do.

FIGS. 3-1, 4A and 4B are schematic views showing an example of a method for producing a resin-encapsulated semiconductor using the release film of the first invention of the present application.
As shown in FIG. 3A, the release film 1 of the first invention of the present application is supplied from the roll-shaped roll into the molding die 2 by the roll 1-2 and the roll 1-3. Next, the release film 1 is disposed on the inner surface of the upper mold 2. If necessary, the inner surface of the upper mold 2 may be evacuated to bring the release film 1 into close contact with the inner surface of the upper mold 2. A semiconductor chip 6 disposed on a substrate is disposed in a lower mold 5 of the molding apparatus, and a sealing resin is disposed on the semiconductor chip 6 or a liquid sealing resin so as to cover the semiconductor chip 6. The sealing resin 4 is accommodated between the upper mold 2 and the lower mold 5 on which the release film 1 that has been sucked and adhered is exhausted. Next, as shown in FIG. 3B, the upper mold 2 and the lower mold 5 are closed with the release film 1 of the first invention of this application, and the sealing resin 4 is cured.

As shown in FIG. 3C, the sealing resin 4 flows into the mold by the mold closing and curing, and the sealing resin 4 flows into the space and is filled and sealed so as to surround the side surface of the semiconductor chip 6. The semiconductor chip 6 is taken out by the upper mold 2 and the lower mold 5 being opened. After the mold is opened and the molded product is taken out, the release film 1 is repeatedly used for a plurality of times or a new release film is supplied and subjected to the next resin molding.

The mold release film of the first invention of the present application is closely attached to the upper mold, interposed between the mold and the sealing resin, and resin molding prevents the resin from adhering to the mold. The molded product can be easily released from the mold.
The release film can be newly supplied and resin-molded for each resin molding operation, or can be newly supplied and resin-molded for each of a plurality of resin molding operations.

The sealing resin may be a liquid resin or a resin that is solid at room temperature, but a sealing material such as a liquid that is liquid at the time of resin sealing can be appropriately employed. Specifically, epoxy resin (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolac type epoxy resin, etc.) is mainly used as the sealing resin material, and polyimide type resin ( Bismaleimide-based), silicone-based resin (thermosetting addition type), or the like that is usually used as a sealing resin can be used. The resin sealing conditions vary depending on the sealing resin to be used, but may be appropriately set, for example, within a range of a curing temperature of 120 ° C. to 180 ° C., a molding pressure of 10 to 50 kg / cm ² , and a curing time of 1 to 60 minutes. it can.

Before and after the step of placing the release film 1 on the inner surface of the molding die 8 and the step of placing the semiconductor chip 6 in the molding die 8 are not particularly limited and may be performed simultaneously. After the placement, the release film 1 may be placed, or after the release film 1 is placed, the semiconductor chip 6 may be placed.

Thus, since the release film 1 has the release layer 1A (and the release layer 1A 'if necessary) having a high release property, the semiconductor package 4-2 can be easily released. Moreover, since the release film 1 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 8 while having excellent followability to the mold shape. For this reason, a sealed semiconductor package having a good external appearance can be obtained without generating wrinkles on the resin-sealed surface of the sealed semiconductor package 4-2 or generating a portion not filled with resin (resin chipping). 4-2 can be obtained.

Further, not only the compression molding method in which the solid sealing resin material 4 is pressurized and heated as shown in FIG. 3-1, but also a transfer molding method in which a fluid sealing resin material is injected as described later. May be.

FIG. 4A and FIG. 4B are schematic views showing a transfer mold method which is an example of a method for producing a resin-encapsulated semiconductor using the release film of the first invention of the present application.

As shown in FIG. 4A, the release film 22 of the first invention of the present application is supplied from the roll-shaped roll into the molding die 28 by the roll 24 and the roll 26 (step a). Next, the release film 22 is disposed on the inner surface 30A of the upper mold 30 (step b). If necessary, the upper mold inner surface 30A may be evacuated to bring the release film 22 into close contact with the upper mold inner surface 30A. Next, the semiconductor chip 34 to be resin-sealed (semiconductor chip 34 fixed to the substrate 34A) is placed in the molding die 28, and the sealing resin material 36 is set (step c), and the mold is clamped ( Step d).

Next, as shown in FIG. 4B, a sealing resin material 36 is injected into the molding die 28 under predetermined heating and pressurizing conditions (step e). The temperature (molding temperature) of the molding die 28 at this time is, for example, 165 to 185 ° C., the molding pressure is, for example, 7 to 12 MPa, and the molding time is, for example, about 90 seconds. And after hold | maintaining for a fixed time, the upper mold | type 30 and the lower mold | type 32 are opened, and the semiconductor package 40 and the release film 22 which were resin-sealed are released simultaneously or sequentially (process f).

Then, as shown in FIG. 5, a desired semiconductor package 44 can be obtained by removing the excess resin portion 42 from the obtained semiconductor package 40. The release film 22 may be used as it is for resin sealing of other semiconductor chips as it is, but each time molding is completed, the roll is operated to feed the film, and a new release film 22 is formed as a molding die. 28 is preferably supplied.

Before and after the step of disposing the release film 22 on the inner surface of the molding die 28 and the step of disposing the semiconductor chip 34 in the molding die 28 are not particularly limited and may be performed simultaneously. After the placement, the release film 22 may be placed, or after the release film 22 is placed, the semiconductor chip 34 may be placed.

Thus, since the release film 22 has the release layer 1A (and the release layer 1A 'if necessary) having a high release property, the semiconductor package 40 can be easily released. Moreover, since the release film 22 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 28 while having excellent followability to the die shape. Therefore, it is possible to obtain the semiconductor package 40 having a good appearance without transferring wrinkles on the resin sealing surface of the semiconductor package 40 or generating a portion not filled with resin (resin chipping).

The release film of the first invention of the present application is not limited to the process of resin-sealing a semiconductor element, but a process of molding and releasing various molded products using a molding die, such as a fiber-reinforced plastic molding and release process, plastic It can also be preferably used in lens molding and mold release processes.

Process Release Film The process release film of the second invention of the present application includes the following four aspects.
(2-1 embodiment)
A release film for process which is a laminated film including a release layer 2A and a heat resistant resin layer 2B,
The contact angle of the release film 2A of the laminated film with respect to water is 90 ° to 130 °, and the surface specific resistance value is 1 × 10 ¹³ Ω / □ or less,
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
(Second embodiment)
A release film for process which is a laminated film including a release layer 2A and a heat resistant resin layer 2B,
The contact angle of the release film 2A of the laminated film with respect to water is 90 ° to 130 °, and the surface specific resistance value is 1 × 10 ¹³ Ω / □ or less,
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
(2-3 embodiment)
A release film for process which is a laminated film including a release layer 2A, a heat-resistant resin layer 2B, and a release layer 2A ′ in this order,
Contact angle with respect to the release layer 2A and water of the releasing layer 2A ', the laminated film is a 130 ° from 90 °, the surface resistivity of the releasing layer 2A is 1 × 10 ¹³ Ω / □ or less Because
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
(2-4 embodiment)
A release film for process which is a laminated film including a release layer 2A, a heat-resistant resin layer 2B, and a release layer 2A ′ in this order,
The contact angle with respect to water of the release layer 2A and the release layer 2A ′ of the laminated film is 90 ° to 130 °, and the surface resistivity of the release layer 2A is 1 × 10 ¹³ Ω / □ or less. Because
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.

As is clear from each of the above embodiments, the release film for process of the second invention of the present application (hereinafter also simply referred to as “release film”) has a release layer 2A having release properties for molded products and molds, and A laminated film including a release layer 2A ′ and a heat-resistant resin layer 2B that supports the release layer as desired, wherein the heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent. .

The process release film of the second invention of the present application is disposed on the inner surface of a molding die when a semiconductor element or the like is resin-sealed inside the molding die. At this time, the release layer 2A of the release film (or the release layer 2A ′ when the release layer 2A ′ is present) may be placed on the resin-sealed semiconductor element or the like (molded product) side. It is preferable to arrange. By disposing the release film of the second invention of the present application, it is possible to easily release the resin-encapsulated semiconductor element and the like from the mold.
The contact angle of the release layer 2A with respect to water is 90 ° to 130 °. By having such a contact angle, the release layer 2A has low wettability and is fixed to the cured sealing resin or the mold surface. Without this, the molded product can be easily released.
The contact angle of the release layer 2A with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.
Further, when the surface specific resistance value of the release layer 2A is 1 × 10 ¹³ Ω / □ or less, adhesion of foreign matter, sealing resin, or the like to the release film can be effectively prevented. The surface resistivity of the release layer 2A is preferably 5 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹² Ω / □ or less, and further preferably 5 × 10 ¹¹ Ω / □ or less.

As described above, since the release layer 2A (in some cases, the release layer 2A ′) is disposed on the molded product side, from the viewpoint of the appearance of the molded product, the release layer 2A (in some cases, the release layer in the resin sealing process). It is preferable to suppress the generation of wrinkles in the mold layer 2A ′). This is because the generated wrinkles are transferred to the molded product and the appearance defect of the molded product is highly likely to occur.

In the second invention of the present application, in order to achieve the above-mentioned object, as the laminated film constituting the process release film, the release layer 2A (and the release layer 2A ′ if necessary) and the release layer are supported. A laminated film including the heat resistant resin layer 2B, wherein a laminated film showing a specific value of the thermal dimensional change rate in the transverse (TD) direction is used, and the polymer antistatic agent is contained as the heat resistant resin layer 2B. A layer including the layer 2B1 is used. Here, the laminated film including the release layer 2A (and the release layer 2A ′ if necessary) and the heat-resistant resin layer 2B that supports the release layer is 23 ° C. to 120 ° C. in the TD direction (lateral direction). The rate of thermal dimensional change from 1 to 23 ° C. in the TD direction (lateral direction) from 23 ° C. to 170 ° C. is 4% or less.
By combining a laminated film in which the rate of thermal dimensional change in the transverse (TD) direction exhibits the above specific value and a heat-resistant resin layer including a layer containing a polymer antistatic agent, the appearance of the molded product is extremely poor. Although the mechanism of effective suppression is not necessarily clear, suppression of wrinkles due to the thermal dimensional change rate in the transverse (TD) direction of the laminated film being the specific value described above, and a polymer antistatic agent It is presumed that the suppression of static electricity and the suppression of the uptake of foreign matters such as powder into the process by having a layer containing ssl have some synergistic effect. That is, since foreign substances such as powder can be the starting point of soot, by suppressing the uptake of foreign substances, the suppression of soot generation becomes more effective, while the soot can be the aggregation point of foreign substances. By suppressing the occurrence of the occurrence, the agglomeration and growth of foreign substances are more effectively suppressed, which has some relationship with the suppression of the appearance defect of the molded product at a high level that could not be predicted by the prior art. Presumed.

As described above, the laminated film including the release layer 2A (and the release layer 2A ′ if necessary) and the heat-resistant resin layer 2B that supports the release layer is obtained from 23 ° C. in the TD direction (lateral direction). The rate of thermal dimensional change up to 120 ° C. is 3% or less, or the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction) is 4% or less. Further, the laminated film has a thermal dimensional change rate of 23% to 120 ° C. in the TD direction (lateral direction) of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The rate is more preferably 4% or less.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). When the rate is 4% or less, generation of wrinkles in the release layer in the resin sealing step or the like can be effectively suppressed. The mechanism that suppresses the occurrence of wrinkles in the release layer is not always clear by using a film having a specific rate of thermal dimensional change in the transverse (TD) direction as a laminated film constituting the release film for the process. However, the use of a laminated film having a relatively small thermal expansion / shrinkage is related to the suppression of the thermal expansion / shrinkage of the release layer 2A (or release layer 2A ′) due to heating / cooling during the process. Presumed to be.

The laminated film constituting the process release film of the second invention of the present application preferably has a thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of 2.5% or less. It is more preferably 0% or less, and further preferably 1.5% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate of −5.0% or more from 23 ° C. to 120 ° C. in the TD direction (lateral direction).
The laminated film constituting the process release film of the second invention of the present application preferably has a thermal dimensional change rate from 23 ° C. to 170 ° C. in the TD direction (lateral direction) of 3.5% or less. It is more preferably 0% or less, and further preferably 2.0% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate of −5.0% or more from 23 ° C. to 170 ° C. in the TD direction (lateral direction).

The mechanism by which the generation of wrinkles in the release layer is more effectively suppressed by using a resin layer in which the thermal dimensional change rate in the transverse (TD) direction exhibits the above specific value as the heat-resistant resin layer 2B is not necessarily clear. However, the thermal expansion / contraction of the release layer 2A (or the release layer 2A ′) due to heating / cooling during the process is suppressed by using the heat-resistant resin layer 2B having a relatively small thermal expansion / contraction. It is presumed to be related.

The release film for a process of the second invention of the present application, which is a laminated film including the release layer 2A (and the release layer 2A ′ if necessary) and the heat-resistant resin layer 2B that supports the release layer, has a TD direction ( It is preferable that the sum of the thermal dimensional change rate in the transverse direction and the thermal dimensional change rate in the MD direction (longitudinal direction during production of the film; hereinafter referred to as “longitudinal direction”) is not more than a specific value.
That is, the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less. On the other hand, the laminated film is the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the vertical (MD) direction. Is preferably −5.0% or more.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction and the longitudinal (MD) direction of the laminated film including the release layer 2A (and optionally the release layer 2A ′) and the heat-resistant resin layer 2B. When the sum of the thermal dimensional change rates from 23 ° C. to 120 ° C. is 6% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.

Further, the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and longitudinal (MD) of the laminated film including the release layer 2A (and the release layer 2A ′ as required) and the heat-resistant resin layer 2B. The sum of the thermal dimensional change rates from 23 ° C. to 170 ° C. in the direction is preferably 7% or less, while the laminated film has a thermal dimension from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The sum of the rate of change and the rate of change in the thermal dimension from 23 ° C. to 170 ° C. in the machine direction (MD) is preferably −5.0% or more.
By the sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction being 7% or less, Generation of wrinkles when mounted on the inner surface of the mold can be further effectively suppressed.

Release layer 2A
The release layer 2A constituting the process release film of the second invention of the present application has a contact angle with water of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115. °, more preferably 100 ° to 110 °. The surface resistivity of the release layer 2A is 1 × 10 ¹³ Ω / □ or less, preferably 5 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹² Ω / □ or less, and more preferably 5 × ^{10 11} Ω / □ is less than or equal to.
In view of excellent mold releasability and availability, it is preferable to include a resin selected from the group consisting of a fluororesin, 4-methyl-1-pentene (co) polymer, and a polystyrene resin.

The fluororesin that can be used for the release layer 2A is the same as that described for the release layer 1A.
The 4-methyl-1-pentene (co) polymer that can be used for the release layer 2A is the same as that described for the release layer 1A.
Furthermore, the polystyrene resin that can be used for the release layer 2A is the same as that described for the release layer 1A.

The release layer 2A preferably has a heat resistance that can withstand the temperature of the mold during molding (typically 120 to 180 ° C.). From this point of view, the release layer 2A preferably includes a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 190 ° C. or higher, and more preferably 200 ° C. or higher and 300 ° C. or lower.
In order to provide crystallinity to the release layer 2A, for example, a fluororesin preferably contains at least a structural unit derived from tetrafluoroethylene, and a 4-methyl-1-pentene (co) polymer has 4-methyl-1 -It preferably contains at least a structural unit derived from pentene, and in a polystyrene resin, it preferably contains at least syndiotactic polystyrene. By including a crystal component in the resin constituting the release layer 2A, it is difficult for wrinkles to occur in the resin sealing process and the like, and it is suitable for suppressing wrinkles from being transferred to a molded product and causing poor appearance. .

The resin containing the crystalline component constituting the release layer 2A has a heat of crystal melting of 15 J / g or more and 60 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221. It is preferable that it is 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, in addition to being able to more effectively express heat resistance and releasability that can withstand hot press molding in the resin sealing step, etc., it also suppresses the dimensional change rate. Therefore, generation of wrinkles can be prevented. On the other hand, if the heat of crystal fusion is 60 J / g or less, the release layer 2A has an appropriate hardness, and therefore, sufficient followability to the mold of the film can be obtained in the resin sealing step or the like. There is no risk of film damage.

The release layer 2A may contain other resin in addition to the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin. In this case, other resins and their contents are the same as those described for the release layer 1A.

In addition to the fluororesin, 4-methyl-1-pentene (co) polymer, and / or polystyrene resin, the release layer 2A includes a heat resistance stabilizer, weather resistance, and the like within a range not impairing the object of the second invention of the present application. You may also contain the well-known additive generally mix | blended with resin for films, such as a stabilizer, a rust prevention agent, a copper-resistant damage stabilizer, and an antistatic agent. The content of these additives can be, for example, 0.0001 to 10 parts by weight with respect to 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 2A is not particularly limited as long as the release property for the molded product is sufficient, but is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer 2A may have a concavo-convex shape as necessary, thereby improving the releasability. The method for imparting irregularities to the surface of the release layer 2A is not particularly limited, but a general method such as embossing can be employed.

Release layer 2A '
The process release film of the second invention of the present application may further have a release layer 2A ′ in addition to the release layer 2A and the heat-resistant resin layer 2B. That is, the process release film of the second invention of the present application may be a process release film that is a laminated film including the release layer 2A, the heat-resistant resin layer 2B, and the release layer 2A ′ in this order. Good.
The contact angle with respect to water of the release layer 2A ′ that may constitute the process release film of the second invention of the present application is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98. It is from ° to 115 °, more preferably from 100 ° to 110 °. The preferable material, configuration, physical properties, and the like of the release layer 2A ′ are the same as those described above for the release layer 2A.
Further, the surface resistivity of the release layer 2A ′ is preferably 1 × 10 ¹³ Ω / □ or less, more preferably 5 × 10 ¹² Ω / □ or less, and further preferably 1 × 10 ¹² Ω / □ or less. Particularly preferably, it is 5 × 10 ¹¹ Ω / □ or less. When the surface specific resistance value of the release layer 2A ′ is in the above range, the adhesion of foreign matters during the process can be more effectively suppressed.

The release layer 2A and the release layer 2A ′ are the same when the release film for process is a laminated film including the release layer 2A, the heat-resistant resin layer 2B, and the release layer 2A ′ in this order. It may be a layer having a different structure or a layer having a different structure.
From the standpoint of preventing warpage and ease of handling due to the same release properties on both surfaces, the release layer 2A and the release layer 2A ′ may have the same or substantially the same configuration. Preferably, from the viewpoint of optimally designing each in relation to the process using the release layer 2A and the release layer 2A ′, for example, the release layer 2A has excellent release properties from the mold. From the viewpoint of making the layer 2A ′ excellent in releasability from the molded product, it is preferable that the release layer 2A and the release layer 2A ′ have different configurations.
When the release layer 2A and the release layer 2A ′ have different configurations, the release layer 2A and the release layer 2A ′ may be made of the same material and have different configurations such as thickness. However, the materials and other configurations may be different.

Heat resistant resin layer 2B
The heat-resistant resin layer 2B constituting the process release film of the second invention of the present application has a function of supporting the release layer 2A (and possibly the release layer 2A ′) and suppressing wrinkles due to mold temperature and the like. Have.
The heat-resistant resin layer 2B constituting the process release film of the second invention of the present application includes a layer 2B1 containing a polymer antistatic agent. Here, “including” the layer 2B1 containing the polymer antistatic agent means that the entire heat resistant resin layer 2B is composed of the layer 2B1 containing the polymer antistatic agent, and the heat resistant resin layer. When a part of 2B is composed of a layer 2B1 containing a polymeric antistatic agent, it is used to include both. Accordingly, the heat resistant resin layer 2B may or may not further include a layer other than the layer 2B1 containing the polymer antistatic agent.

The heat-resistant resin layer 2B constituting the process release film of the second invention of the present application includes a layer 2B1 containing a polymer antistatic agent, thereby providing a surface of the release layer 2A (and optionally the release layer 2A ′). The specific resistance value is low and contributes to prevention of charging.
By the presence of the layer 2B1 containing the polymer antistatic agent, the antistatic property is effectively expressed also on the surface of the release film for process of the second invention of the present application. Therefore, the adhesion of foreign matters such as dust due to static electricity can be effectively suppressed, and even when a part of a semiconductor element is in direct contact with the process release film, for example, when manufacturing a semiconductor package, the process release film The destruction of the semiconductor element due to charging-discharging can be effectively suppressed.
The surface resistance value of the heat resistant resin layer 2B is preferably as low as possible from the viewpoint of antistatic, and the lower limit is not particularly limited. The surface resistance value of the heat-resistant resin layer 2B tends to decrease as the conductive performance of the polymer antistatic agent increases and as the content of the polymer antistatic agent increases.

As another layer other than the layer 2B1 containing the polymer antistatic agent, for example, an adhesive layer 2B2 containing an adhesive can be preferably used. That is, the heat resistant resin layer 2B may include a layer 2B1 containing a polymer antistatic agent and an adhesive layer 2B2 containing an adhesive.
In this case, the heat-resistant resin layer 2B may be composed of only the layer 2B1 containing a polymer antistatic agent and the adhesive layer 2B2 containing an adhesive, or a layer containing a polymer antistatic agent. Other layers other than 2B1 and the adhesive layer 2B2 containing an adhesive, for example, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas barrier layer, and the like may be further included.

In the process release film of the second invention of the present application, the rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 2B is 3% or less, or the width of the heat-resistant resin layer 2B It is preferable that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the (TD) direction is 3% or less. Further, the heat resistant resin layer 2B has a thermal dimensional change rate of 23% to 120 ° C. in the transverse (TD) direction of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction. The rate is more preferably 3% or less.
Although any resin layer including an unstretched film can be used for the heat-resistant resin layer 2B, it is particularly preferable to comprise a stretched film.
The stretched film tends to have a low or negative coefficient of thermal expansion due to the influence of stretching in the manufacturing process, and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction is 3% or less. Alternatively, since it is relatively easy to realize the characteristic that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 2B is 3% or less, the heat resistant resin layer 2B It can be preferably used.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 2B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.
The thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer 2B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.

Details of the stretched film are the same as those described for the heat resistant resin layer 1B.

The heat-resistant resin layer 2B has heat resistance that can withstand the mold temperature during molding (typically 120 to 180 ° C.) from the viewpoint of controlling the strength of the film and the rate of thermal dimensional change within an appropriate range. It is preferable. From this viewpoint, the heat-resistant resin layer 2B preferably includes a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 ° C. or higher, and the melting point is 155 ° C. or higher and 300 ° C. or lower. Is more preferably 185 to 210 ° C., and particularly preferably 185 to 205 ° C.

As described above, the heat resistant resin layer 2B preferably contains a crystalline resin having a crystalline component. As the crystalline resin to be contained in the heat-resistant resin layer 2B, for example, a crystalline resin such as a polyester resin, a polyamide resin, or a polypropylene resin can be used for a part or all thereof. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the crystalline resin in the heat-resistant resin layer 2B, it is more advantageous to prevent wrinkles from being generated in the resin sealing process and the like and to suppress the appearance of defects due to transfer of wrinkles to the molded product. Become.
The resin constituting the heat-resistant resin layer 2B preferably has a heat of crystal melting of 20 J / g or more and 100 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221. It is more preferably 25 J / g or more and 65 J / g or less, more preferably 25 J / g or more and 55 J / g or less, more preferably 28 J / g or more and 50 J / g or less, and more preferably 28 J / g g or more and 40 J / g or less is more preferable, and 28 J / g or more and 35 J / g or less is more preferable. When it is 20 J / g or more, it is possible to effectively exhibit heat resistance and releasability that can withstand hot press molding in a resin sealing process and the like, and the dimensional change rate can be slightly suppressed. The occurrence of wrinkles can also be prevented. On the other hand, since the crystal heat of fusion is 100 J / g or less, it is possible to impart an appropriate hardness to the heat-resistant resin layer 2B, so that sufficient followability of the film to the mold is ensured in the resin sealing step and the like. In addition to being able to do so, there is no risk of the film being easily damaged. In the present embodiment, the crystal melting calorie is the calorific value (J / g) on the vertical axis obtained in the first heating step in the differential scanning calorimetry (DSC) measurement according to JISK7221 and the horizontal axis. In the chart showing the relationship with temperature (° C.), it is a numerical value obtained by the sum of peak areas having a peak at 120 ° C. or higher.
The heat of crystal fusion of the heat-resistant resin layer 2B can be adjusted by appropriately setting the heating and cooling conditions and the stretching conditions during film production.

The thickness of the heat-resistant resin layer 2B is not particularly limited as long as the film strength can be secured, but is usually 1-1.
It is 00 μm, preferably 5 to 50 μm.

Layer 2B1 containing a polymeric antistatic agent
It is known that the polymer antistatic agent in the layer 2B1 containing a polymer antistatic agent that is suitably used in the heat resistant resin layer 2B constituting the laminate of the second invention of the present application has an antistatic function. The high molecular compound which can be used can be used. For example, a cationic copolymer having a quaternary ammonium base in the side group, an anionic compound containing polystyrene sulfonic acid, a compound having a polyalkylene oxide chain (a polyethylene oxide chain or a polypropylene oxide chain is preferred), a polyethylene glycol methacrylate copolymer. Examples thereof include nonionic polymers such as polymers, polyether ester amides, polyether amide imides, polyether esters, ethylene oxide-epichlorohydrin copolymers, and π-conjugated conductive polymers. These may be used alone or in combination of two or more.

The quaternary ammonium base in the copolymer having a quaternary ammonium base in the side group has an effect of imparting dielectric polarization and rapid dielectric polarization relaxation due to conductivity.
The copolymer preferably has a carboxy group together with a quaternary ammonium base in the side group. When it has a carboxy group, the copolymer has crosslinkability and can form the intermediate layer 4 alone. Further, when used in combination with an adhesive such as a urethane-based adhesive, it reacts with the adhesive to form a crosslinked structure, and the adhesiveness, durability, and other mechanical properties can be significantly improved.
The copolymer may further have a hydroxy group as a side group. The hydroxy group has an effect of increasing adhesiveness by reacting with a functional group in the adhesive such as an isocyanate group.

The copolymer can be obtained by copolymerizing monomers having the above functional groups. Specific examples of the monomer having a quaternary ammonium base include dimethylaminoethyl acrylate quaternized compounds (including anions such as chloride, sulfate, sulfonate, and alkyl sulfonate as counter ions). Specific examples of the monomer having a carboxy group include (meth) acrylic acid, (meth) acryloyloxyethyl succinic acid, phthalic acid, hexahydrophthalic acid and the like.
Other monomers other than these can also be copolymerized. Examples of the other monomer include vinyl derivatives such as alkyl (meth) acrylate, styrene, vinyl acetate, vinyl halide, and olefin.

The ratio of copolymer units having each functional group in the copolymer can be set as appropriate. The proportion of copolymerized units having a quaternary ammonium base is preferably 15 to 40 mol% with respect to the total of all copolymerized units. When this proportion is 15 mol% or more, the antistatic effect is excellent. If it exceeds 40 mol%, the hydrophilicity of the copolymer may be too high. The proportion of units having a carboxy group is preferably 3 to 13 mol% with respect to the total of all units.

When the copolymer has a carboxy group as a side group, a crosslinking agent (curing agent) may be added to the copolymer. Examples of the crosslinking agent include bifunctional epoxy compounds such as glycerin diglycidyl ether, trifunctional epoxy compounds such as trimethylolpropane triglycidyl ether, and polyfunctional compounds such as ethyleneimine compounds such as trimethylolpropane triaziridinyl ether.
An imidazole derivative such as 2-methylimidazole, 2-ethyl, 4-methylimidazole, and other amines may be added to the copolymer as a ring-opening reaction catalyst for the bifunctional or trifunctional epoxy compound.

The π-conjugated conductive polymer is a conductive polymer having a main chain in which π conjugation is developed. As the π-conjugated conductive polymer, known ones can be used, and examples thereof include polythiophene, polypyrrole, polyaniline, and derivatives thereof.

As the polymer antistatic agent, one produced by a known method may be used, or a commercially available one may be used. For example, as a commercial product of PEDOT polythiophene resin, “MC-200” manufactured by Kaken Sangyo Co., Ltd. may be mentioned.

Preferable embodiments of the layer 2B1 containing the polymer antistatic agent include the following layers (1) and (2).
Layer (1): The polymer antistatic agent itself has a film-forming ability, and the polymer antistatic agent is applied as it is or dissolved in a solvent and wet-coated, and dried if necessary. Layer.
Layer (2): A layer formed by melt-coating the polymer antistatic agent, wherein the polymer antistatic agent itself has film-forming ability and can be melted.

In the layer (1), the polymer antistatic agent itself has film-forming ability means that the polymer antistatic agent is soluble in a solvent such as an organic solvent, and the solution is applied wet and dried. This means that a film is formed.
In the layer (2), the fact that the polymer antistatic agent itself can be melted means that it is melted by heating.

The polymer antistatic agent in the layer (1) may have crosslinkability or may not have crosslinkability. When the polymer antistatic agent has crosslinkability, a crosslinker may be used in combination.
Examples of the polymer antistatic agent having film forming ability and crosslinkability include a copolymer having a quaternary ammonium base and a carboxy group in the side group.
Examples of the cross-linking agent include those described above.
The thickness of the layer (1) is preferably from 0.01 to 1.0 μm, particularly preferably from 0.03 to 0.5 μm. When the thickness of the layer (1) is 0.01 μm or more, a sufficient antistatic effect can be easily obtained, and when it is 1.0 μm or less, sufficient adhesiveness can be obtained during lamination. It becomes easy.
Examples of the polymer antistatic agent in the layer (2) include polyolefin resins containing a surfactant and carbon black. Examples of commercially available products include Peletron HS (manufactured by Sanyo Chemical Industries). The preferable range of the thickness of the layer (2) is the same as the preferable range of the thickness of the layer (1).

The layer 2B1 containing the polymer antistatic agent may be one layer or two or more layers. For example, it may have only one of the layers (1) to (2), or may have both the layer (1) and the layer (2).
As the layer 2B1 containing the polymer antistatic agent, the layer (1) is preferable because it is easy to produce. Layer (1) and layer (2) may be used in combination.

Adhesive layer 2B2
As the adhesive contained in the adhesive layer 2B2 that is preferably used in the heat-resistant resin layer 2B constituting the laminate of the second invention of the present application, a conventionally known adhesive can be appropriately used. From the viewpoint of production efficiency of the laminate of the second invention of the present application, an adhesive for dry lamination can be preferably used. For example, a polyvinyl acetate adhesive; a homopolymer or copolymer of an acrylic ester (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or an acrylic ester and another monomer (methacrylic ester) Polyacrylate adhesives consisting of copolymers with methyl acid, acrylonitrile, styrene, etc .; Cyanoacrylate adhesives; Ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic) An ethylene copolymer adhesive comprising a copolymer with an acid, etc .; a cellulose adhesive; a polyester adhesive; a polyamide adhesive; a polyimide adhesive; an amino resin comprising a urea resin or a melamine resin, etc. Adhesives; phenolic resin adhesives; epoxy adhesives; polyols (polyether polyols) Polyurethane adhesive that crosslinks with isocyanate and / or isocyanurate; reactive (meth) acrylic adhesive; rubber adhesive composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc .; silicone Adhesives such as inorganic adhesives made of alkali metal silicate, low-melting glass, etc .; other adhesives can be used.

Other layers The release film for process of the second invention of the present application has layers other than the release layer 2A, the heat-resistant resin layer 2B, and the release layer 2A ′ as long as the object of the second invention of the present application is not violated. May be. Details of these other layers are the same as those described for the first invention of the present application.

The total thickness of the process release film of the second invention of the present application is not particularly limited, but is preferably 10 to 300 μm, for example, and more preferably 30 to 150 μm. When the total thickness of the release film is in the above range, it is preferable because the handling property when used as a roll is good and the amount of discarded film is small.

Hereinafter, preferred embodiments of the process release film of the second invention of the present application will be described in more detail. FIG. 1 is a schematic diagram showing an example of a three-layer process release film. As shown in FIG. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one surface of the release film 16 with an adhesive layer 14 interposed therebetween.

The release layer 16 is the aforementioned release layer 2A, the heat-resistant resin layer 12 is the aforementioned heat-resistant resin layer 2B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing process; the heat-resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the mold in the sealing process.

FIG. 2 is a schematic diagram showing an example of a five-layer process release film. Members having the same functions as those in FIG. 1 are denoted by the same reference numerals. As shown in FIG. 2, the release film 20 includes a heat resistant resin layer 12 and a release layer 16 A and a release layer 16 B formed on both surfaces of the release film 16 via an adhesive layer 14. The release layer 16A is the aforementioned release layer 2A, the heat-resistant resin layer 12 is the aforementioned heat-resistant resin layer 2B, the release layer 16B is the aforementioned release layer 2A ', and the adhesive layer 14 is the aforementioned It is an adhesive layer.

The compositions of the release layers 16A and 16B may be the same as or different from each other. The thicknesses of the release layers 16A and 16B may be the same as or different from each other. However, it is preferable that the release layers 16A and 16B have the same composition and thickness as each other because a symmetric structure is obtained and the release film itself is hardly warped. In particular, since the release film of the second invention of the present application may be stressed by heating in the sealing process, it is preferable to suppress warping. As described above, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good release properties can be obtained on both the molded product and the inner surface of the mold.

Process Release Film Production Method The process release film of the second invention of the present application can be produced by any method, but the preferred production method is the same as that described for the first invention of the present application.

Manufacturing Process The mold release film of the second invention of the present application is used by placing a semiconductor chip or the like in the mold and injecting and molding the resin between the semiconductor chip and the inner surface of the mold. Can do. By using the process release film of the second invention of the present application, it is possible to effectively prevent mold release failure from the mold, generation of burrs, and the like.
The resin used in the manufacturing process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the technical field, and in particular, epoxy-based thermosetting resins are used. It is preferable to use it.
As the above manufacturing process, semiconductor chip sealing is the most representative, but it is not limited to this. The second invention of the present application is also applicable to a fiber reinforced plastic molding process, a plastic lens molding process, and the like. Can do.

3, 4A and 4B are schematic views showing an example of a method for producing a resin-encapsulated semiconductor using the release film of the second invention of the present application.
As shown in FIG. 3a, the release film 1 of the second invention of the present application is supplied from the roll-shaped roll into the molding die 2 by the roll 1-2 and the roll 1-3. Next, the release film 1 is disposed on the inner surface of the upper mold 2. If necessary, the inner surface of the upper mold 2 may be evacuated to bring the release film 1 into close contact with the inner surface of the upper mold 2. A semiconductor chip 6 disposed on a substrate is disposed in the lower mold 5 of the molding apparatus, and a granular sealing resin 4 as shown in FIG. Alternatively, although not shown, a liquid sealing resin is injected so as to cover the semiconductor chip 6 as an alternative, so that the upper mold 2 and the lower mold 5 are arranged with the release film 1 that is exhausted and sucked into close contact. A sealing resin is accommodated therebetween. Next, as shown in FIG. 3b, the upper mold 2 and the lower mold 5 are closed via the release film 1 of the second invention of the present application, and preferably a granular seal as shown in the figure. The resin is cured.

As shown in FIG. 3 c, the sealing resin 4 is fluidized in the mold by mold closing and curing, and the sealing resin 4 flows into the space and fills and surrounds the side surface of the semiconductor chip 6. The chip 6 is taken out by the upper mold 2 and the lower mold 5 being opened. After the mold is opened and the molded product is taken out, the release film 1 is repeatedly used for a plurality of times or a new release film is supplied and subjected to the next resin molding.

The mold release film of the second invention of the present application is closely attached to the upper mold, interposed between the mold and the sealing resin, and resin molding prevents the resin from adhering to the mold. The molded product can be easily released from the mold.
The release film can be newly supplied and resin-molded for each resin molding operation, or can be newly supplied and resin-molded for each of a plurality of resin molding operations.

The sealing resin may be a liquid resin or a solid resin at room temperature, for example, a granular resin, but a sealing material such as a liquid that is liquid at the time of resin sealing can be appropriately employed. Specifically, epoxy resin (biphenyl type epoxy resin, bisphenol epoxy resin, o-cresol novolac type epoxy resin, etc.) is mainly used as the sealing resin material, and polyimide type resin ( Bismaleimide-based), silicone-based resin (thermosetting addition type), or the like that is usually used as a sealing resin can be used. The resin sealing conditions vary depending on the sealing resin to be used, but may be appropriately set, for example, within a range of a curing temperature of 120 ° C. to 180 ° C., a molding pressure of 10 to 50 kg / cm ² , and a curing time of 1 to 60 minutes. it can.

Thus, since the release film 1 has the release layer 2A (and the release layer 2A 'if necessary) having a high release property, the semiconductor package 4-2 can be easily released. Moreover, since the release film 1 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 8 while having excellent followability to the mold shape. For this reason, a sealed semiconductor package having a good external appearance can be obtained without generating wrinkles on the resin-sealed surface of the sealed semiconductor package 4-2 or generating a portion not filled with resin (resin chipping). 4-2 can be obtained. Moreover, since the surface resistance of the release film 1 is relatively small, it is possible to effectively suppress appearance defects caused by adhesion of granular sealing resin to the release film due to static electricity.

Further, as shown in FIG. 3, the transfer is not limited to the compression molding method in which the solid sealing resin material 4 preferably in the form of granules is pressurized and heated, and the sealing resin material in a fluid state is injected as described later. A molding method may be adopted.

4A and 4B are schematic views showing a transfer mold method which is an example of a method for producing a resin-encapsulated semiconductor using the release film of the second invention of the present application.

As shown in FIG. 4A, the release film 22 of the second invention of the present application is supplied from a roll-shaped roll into a molding die 28 by a roll 24 and a roll 26 (step a). Next, the release film 22 is disposed on the inner surface 30A of the upper mold 30 (step b). If necessary, the upper mold inner surface 30A may be evacuated to bring the release film 22 into close contact with the upper mold inner surface 30A. Next, the semiconductor chip 34 to be resin-sealed (semiconductor chip 34 fixed to the substrate 34A) is placed in the molding die 28, and the sealing resin material 36 is set (step c), and the mold is clamped ( Step d).

Thus, since the release film 22 has the release layer 2A (and the release layer 2A 'if desired) having a high release property, the semiconductor package 40 can be easily released. Moreover, since the release film 22 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 28 while having excellent followability to the die shape. Therefore, it is possible to obtain the semiconductor package 40 having a good appearance without transferring wrinkles on the resin sealing surface of the semiconductor package 40 or generating a portion not filled with resin (resin chipping).

The release film of the second invention of the present application is not limited to a step of resin-sealing a semiconductor element, but a step of molding and releasing various molded products using a molding die, such as a fiber reinforced plastic molding and release step, a plastic It can also be preferably used in lens molding and mold release processes.

Process Release Film The process release film of the third invention of the present application includes the following four aspects.
(Aspect 3-1)
A release film for process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
(Aspect 3-2)
A release film for process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
(3-3 type)
A release film for process which is a laminated film including the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ in this order,
The contact angle for water of the release layer 3A and the release layer 3A ′ is 90 ° to 130 °, and the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa. Mold film.
(Aspect 3-4)
A release film for process which is a laminated film including the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ in this order,
The contact angle for water of the release layer 3A and the release layer 3A ′ is 90 ° to 130 °, and the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa. Mold film.

As is clear from each of the above embodiments, the release film for process of the third invention of the present application (hereinafter also simply referred to as “release film”) has a release layer 3A having release properties for molded products and molds, and A laminated film including a release layer 3A ′ and a heat-resistant resin layer 3B that supports the release layer as desired.

The process release film of the third invention of the present application is disposed on the inner surface of the molding die when a semiconductor element or the like is resin-sealed inside the molding die. At this time, the release layer 3A of the release film (may be the release layer 3A ′ when the release layer 3A ′ is present) is placed on the resin-sealed semiconductor element or the like (molded product) side. It is preferable to arrange. By disposing the release film of the third invention of the present application, the resin-sealed semiconductor element or the like can be easily released from the mold.
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °. By having such a contact angle, the release layer 3A has low wettability and is fixed to the cured sealing resin or the mold surface. Without this, the molded product can be easily released.
The contact angle of the release layer 3A with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.

As described above, the release layer 3A (in some cases, the release layer 3A ′) is disposed on the molded product side, so that the mold in the release layer 3A (in some cases, the release layer 3A ′) in the resin sealing process. It is preferable to suppress the occurrence of. This is because if wrinkles occur in the release layer 3A (release layer 3A 'in some cases), the generated wrinkles are transferred to the molded product, and there is a high possibility that the appearance defect of the molded product will occur.

In the third invention of the present application, in order to achieve the above object, the release layer 3A (and the release layer 3A ′ as required) and the release layer are supported as a laminated film constituting the process release film. A laminated film including the heat-resistant resin layer 3B and having a specific value for the tensile elastic modulus is used.
That is, the laminated film including the release layer 3A (and the release layer 3A ′ if necessary) and the heat-resistant resin layer 3B that supports the release layer has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa. Or a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa. Furthermore, the laminated film preferably has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa, and a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
When the tensile elastic modulus at 120 ° C. of the laminated film is from 75 MPa to 500 MPa, or the tensile elastic modulus at 170 ° C. is from 75 MPa to 500 MPa, generation of wrinkles in the release layer in the resin sealing process or the like It can be effectively suppressed. The mechanism by which the generation of wrinkles in the release layer is suppressed when the tensile modulus at a specific temperature of the laminated film constituting the release film for the process exhibits the above specific value is not necessarily clear, but it is heated during the process. It has a tensile modulus of elasticity above a certain value in a state where it has been suppressed, and deformation that leads to generation of wrinkles is suppressed, and having a tensile modulus of elasticity below a certain value is related to the dispersion of strain It is guessed. If it exceeds 500 MPa, the mold followability is inferior, so that it is difficult to fill the sealing resin at the end portion, and there is a high possibility of appearance defects such as occurrence of resin chipping.

The laminated film constituting the process release film of the third invention of the present application preferably has a tensile elastic modulus at 120 ° C. of 80 MPa to 400 MPa,
More preferably from 85 MPa to 350 MPa,
More preferably, it is 88 MPa to 300 MPa,
It is particularly preferable that the pressure is 90 MPa to 280 MPa.
The laminated film constituting the process release film of the third invention of the present application preferably has a tensile elastic modulus at 170 ° C. of 80 MPa to 400 MPa,
More preferably from 85 MPa to 350 MPa,
More preferably from 88 MPa to 300 MPa, more preferably from 90 MPa to 280 MPa, still more preferably from 95 MPa to 200 MPa,
It is particularly preferable that the pressure is 105 MPa to 170 MPa.
The laminated film constituting the process release film of the third invention of the present application is free during processing that the tensile elastic modulus at 120 ° C. and the tensile elastic modulus at 170 ° C. are both within the above preferred range. It is particularly preferred because of its wide range of uses and applications.

In addition, the laminated film including the release layer 3A (and the release layer 3A ′ if necessary) and the heat-resistant resin layer 3B that supports the release layer is from 23 ° C. to 120 ° C. in the TD direction (lateral direction). It is preferable that the thermal dimensional change rate is 3% or less, or the thermal dimensional change rate from 23 ° C. to 170 ° C. in the TD direction (lateral direction) is 4% or less. Further, the laminated film has a thermal dimensional change rate of 23% to 120 ° C. in the TD direction (lateral direction) of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The rate is more preferably 4% or less.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). When the rate is 4% or less, generation of wrinkles in the release layer in the resin sealing step or the like can be further effectively suppressed. In this embodiment, as the laminated film constituting the process release film, the film having a specific rate of thermal dimensional change in the transverse (TD) direction described above is used to further effectively suppress generation of wrinkles in the release layer. The mechanism of the release layer 3A (or the release layer 3A ′) due to heating / cooling during the process can be reduced by using a laminated film having a relatively small thermal expansion / shrinkage. It is presumed to be related to being suppressed.

The laminated film constituting the process release film of this embodiment preferably has a thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of 2.5% or less. % Or less, more preferably 1.5% or less. On the other hand, the laminated film preferably has a thermal dimensional change rate of −5.0% or more from 23 ° C. to 120 ° C. in the TD direction (lateral direction).
The laminated film constituting the process release film of the present embodiment preferably has a thermal dimensional change rate from 23 ° C. to 170 ° C. in the TD direction (lateral direction) of 3.5% or less. % Or less is more preferable, and 2.0% or less is still more preferable. On the other hand, the laminated film preferably has a thermal dimensional change rate of −5.0% or more from 23 ° C. to 170 ° C. in the TD direction (lateral direction).

The release film for a process of the third invention of the present application, which is a laminated film including the release layer 3A (and the release layer 3A ′ if necessary) and the heat-resistant resin layer 3B that supports the release layer, has a TD direction ( It is preferable that the sum of the thermal dimensional change rate in the transverse direction and the thermal dimensional change rate in the MD direction (longitudinal direction during production of the film; hereinafter referred to as “longitudinal direction”) is not more than a specific value.
That is, the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less. On the other hand, the laminated film is the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the vertical (MD) direction. Is preferably −5.0% or more.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction and the longitudinal (MD) direction of the laminated film including the release layer 3A (and the release layer 3A ′ if necessary) and the heat-resistant resin layer 3B. When the sum of the thermal dimensional change rates from 23 ° C. to 120 ° C. is 6% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.

Further, the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and longitudinal (MD) of the laminated film including the release layer 3A (and release layer 3A ′ if necessary) and the heat-resistant resin layer 3B. The sum of the thermal dimensional change rates from 23 ° C. to 170 ° C. in the direction is preferably 7% or less, while the laminated film has a thermal dimension from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The sum of the rate of change and the rate of change in the thermal dimension from 23 ° C. to 170 ° C. in the machine direction (MD) is preferably −5.0% or more.
By the sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction being 7% or less, Generation of wrinkles when mounted on the inner surface of the mold can be further effectively suppressed.

Release layer 3A
The release layer 3A constituting the process release film of the third invention of the present application has a contact angle with water of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115. °, more preferably 100 ° to 110 °. In view of excellent mold releasability and availability, it is preferable to include a resin selected from the group consisting of a fluororesin, 4-methyl-1-pentene (co) polymer, and a polystyrene resin.

The fluororesin that can be used for the release layer 3A may be a resin containing a structural unit derived from tetrafluoroethylene. Although it may be a homopolymer of tetrafluoroethylene, it may be a copolymer with other olefins. Examples of other olefins include ethylene. A copolymer containing tetrafluoroethylene and ethylene as monomer constitutional units is a preferred example. In such a copolymer, the proportion of constitutional units derived from tetrafluoroethylene is 55 to 100% by mass. The proportion of the structural unit derived from is preferably 0 to 45% by mass.

The 4-methyl-1-pentene (co) polymer that can be used for the release layer 3A may be a homopolymer of 4-methyl-1-pentene, and 4-methyl-1-pentene, It may be a copolymer with other olefins having 2 to 20 carbon atoms (hereinafter referred to as “olefins having 2 to 20 carbon atoms”).

Polystyrene resins that can be used for the release layer 3A include styrene homopolymers and copolymers, and the structural unit derived from styrene contained in the polymer is at least 60% by weight or more. Preferably, it is 80% by weight or more.
The polystyrene resin may be isotactic polystyrene or syndiotactic polystyrene, but is preferably isotactic polystyrene from the viewpoint of transparency, availability, release properties, heat resistance, etc. From this point of view, syndiotactic polystyrene is preferable. Polystyrene may be used alone or in combination of two or more.

The release layer 3A preferably has heat resistance that can withstand the mold temperature during molding (typically 120 to 180 ° C.). From this point of view, the release layer 3A preferably includes a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 190 ° C. or higher, and more preferably 200 ° C. or higher and 300 ° C. or lower.
In order to bring the release layer 3A to crystallinity, for example, a fluororesin preferably contains at least a structural unit derived from tetrafluoroethylene. In a 4-methyl-1-pentene (co) polymer, 4-methyl-1 -It preferably contains at least a structural unit derived from pentene, and in a polystyrene resin, it preferably contains at least syndiotactic polystyrene. By including a crystal component in the resin constituting the release layer 3A, it is difficult for wrinkles to occur in the resin sealing process and the like, and it is suitable for suppressing wrinkles from being transferred to a molded product to cause poor appearance. .

The resin containing the crystalline component constituting the release layer 3A has a heat of crystal melting of 15 J / g or more and 60 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221. It is preferable that it is 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, in addition to being able to more effectively express heat resistance and releasability that can withstand hot press molding in the resin sealing step, etc., it also suppresses the dimensional change rate. Therefore, generation of wrinkles can be prevented. On the other hand, if the heat of crystal fusion is 60 J / g or less, the release layer 3A has an appropriate hardness, so that sufficient followability to the mold of the film can be obtained in the resin sealing step or the like. There is no risk of film damage.

The release layer 3A may further contain other resins in addition to the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin. In this case, it is preferable that the hardness of the other resin is relatively high. Examples of other resins include polyamide-6, polyamide-66, polybutylene terephthalate, and polyethylene terephthalate. As described above, even when the release layer 3A contains a large amount of soft resin (for example, when the 4-methyl-1-pentene copolymer contains a large amount of olefins having 2 to 20 carbon atoms), the hardness of the release layer 3A is relatively high. By further including a high resin, the release layer 3A can be hardened, which is advantageous in suppressing wrinkles in the sealing process and the like.

The content of these other resins is preferably, for example, 3 to 30% by mass with respect to the resin component constituting the release layer 3A. By setting the content of other resins to 3 mass or more, the effect of addition can be made substantial, and by setting the content to 30 mass% or less, the releasability for a mold or a molded product is maintained. be able to.

In addition to the fluororesin, 4-methyl-1-pentene (co) polymer, and / or polystyrene resin, the release layer 3A includes a heat resistance stabilizer, weather resistance, and the like within a range not impairing the object of the third invention of the present application. You may also contain the well-known additive generally mix | blended with resin for films, such as a stabilizer, a rust prevention agent, a copper-resistant damage stabilizer, and an antistatic agent. The content of these additives can be, for example, 0.0001 to 10 parts by weight with respect to 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 3A is not particularly limited as long as the release property to the molded product is sufficient, but is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer 3A may have a concavo-convex shape as necessary, thereby improving the releasability. The method for imparting irregularities to the surface of the release layer 3A is not particularly limited, but a general method such as embossing can be employed.

Release layer 3 A '
The process release film of the third invention of the present application may further include a release layer 3A ′ in addition to the release layer 3A and the heat-resistant resin layer 3B. That is, the process release film of the third invention of the present application may be a process release film that is a laminated film including the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ in this order. Good.
The contact angle with respect to water of the release layer 3A ′ that may constitute the process release film of the third invention of the present application is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98. It is from ° to 115 °, more preferably from 100 ° to 110 °. The preferable material, configuration, physical properties, and the like of the release layer 3A ′ are the same as those described above for the release layer 3A.

The release layer 3A and the release layer 3A ′ are the same when the release film for process is a laminated film including the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ in this order. It may be a layer having a different structure or a layer having a different structure.
From the standpoints of warpage prevention and ease of handling due to the same release properties on both surfaces, the release layer 3A and the release layer 3A ′ may have the same or substantially the same configuration. Preferably, from the viewpoint of optimally designing each in relation to the process of using the release layer 3A and the release layer 3A ′, for example, the release layer 3A has excellent release properties from the mold. From the viewpoint of making the layer 3A ′ excellent in releasability from the molded product, it is preferable that the release layer 3A and the release layer 3A ′ have different configurations.
In the case where the release layer 3A and the release layer 3A ′ have different configurations, the release layer 3A and the release layer 3A ′ may be made of the same material and have different configurations such as thickness. However, the materials and other configurations may be different.

Heat resistant resin layer 3 B
The heat-resistant resin layer 3B constituting the process release film of the third invention of the present application has a function of supporting the release layer 3A (and possibly the release layer 3A ′) and suppressing wrinkles due to mold temperature and the like. Have.
In the release film for process according to the third invention of the present application, the rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less, or the transverse direction of the heat resistant resin layer 3B. It is preferable that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the (TD) direction is 3% or less. Further, the heat resistant resin layer 3B has a thermal dimensional change rate of 23% to 120 ° C. in the transverse (TD) direction of 3% or less and a thermal dimension from 23 ° C. to 170 ° C. in the transverse (TD) direction. The change rate is more preferably 3% or less.
Thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less, or heat from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 3B When the dimensional change rate is 3% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.
The mechanism by which the generation of wrinkles in the release layer is more effectively suppressed by using a resin layer in which the thermal dimensional change rate in the transverse (TD) direction exhibits the above specific value as the heat-resistant resin layer 3B is not necessarily clear. However, the thermal expansion / contraction of the release layer 3A (or the release layer 3A ′) due to heating / cooling during the process is suppressed by using the heat-resistant resin layer 3B having relatively small thermal expansion / contraction. It is presumed to be related.

Although any resin layer including an unstretched film can be used for the heat resistant resin layer 3B, it is particularly preferable that the heat resistant resin layer 3B comprises a stretched film.
The stretched film tends to have a low or negative coefficient of thermal expansion due to the influence of stretching in the manufacturing process, and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction is 3% or less. Alternatively, since it is relatively easy to realize the characteristic that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 3B is 3% or less, the heat resistant resin layer 3B It can be preferably used.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 3B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.
The thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer 3B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.

In the release film for process of the third invention of the present application, the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 3B and the heat from 23 ° C. to 120 ° C. in the longitudinal (MD) direction. The sum of the dimensional change rates is 6% or less, or the thermal dimensional change rate in the transverse (TD) direction from 23 ° C. to 170 ° C. and the longitudinal (MD) direction from 23 ° C. to 170 ° C. The sum of the thermal dimensional change rates is preferably 5% or less. The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 3B and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction is 6% or less, and The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer 3B and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the vertical (MD) direction is 5% or less. Is more preferable. When the sum of the thermal dimensional change rate in the transverse (TD) direction and the thermal dimensional change rate in the longitudinal (MD) direction of the heat-resistant resin layer 3B is within the above range, generation of wrinkles when mounted on the inner surface of the mold is further increased. It can be effectively suppressed.
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat resistant resin layer 3B is −3.0% or more. It is more preferably 5.0% or less, and further preferably -2.0% or more and 4.5% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat-resistant resin layer 3B and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the vertical (MD) direction is −15.5% or more. It is more preferably 5.0% or less, and further preferably -10.0% or more and 4.5% or less.
From the viewpoint of keeping the sum of the thermal dimensional change rate in the transverse (TD) direction and the thermal dimensional change rate in the longitudinal (MD) direction of the heat-resistant resin layer 3B within the above range, it is advantageous to use a stretched film. It is particularly advantageous to control the conditions appropriately.

As the stretched film, a stretched film selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film is preferably used. These stretched films are relatively easy to reduce the thermal expansion coefficient in the transverse (TD) direction or to be negative by stretching, and the mechanical properties are suitable for use in the third invention of the present application. Moreover, since it is relatively easy to obtain at low cost, it is particularly suitable as a stretched film in the heat-resistant resin layer 3B.

The heat-resistant resin layer 3B has heat resistance that can withstand the mold temperature (typically 120 to 180 ° C.) at the time of molding from the viewpoint of controlling the strength of the film and the rate of thermal dimensional change within an appropriate range. It is preferable. From this point of view, the heat resistant resin layer 3B preferably includes a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 ° C. or higher, and the melting point is 155 ° C. or higher and 300 ° C. or lower. Is more preferably 185 to 210 ° C., and particularly preferably 185 to 205 ° C.

As described above, the heat resistant resin layer 3B preferably contains a crystalline resin having a crystalline component. As the crystalline resin to be contained in the heat resistant resin layer 3B, for example, a crystalline resin such as a polyester resin, a polyamide resin, or a polypropylene resin can be used for part or all of the crystalline resin. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the crystalline resin in the heat-resistant resin layer 3B, it is less likely that wrinkles are generated in the resin sealing process and the like, and it is more advantageous to suppress the appearance of defects due to transfer of wrinkles to a molded product. Become.
The resin constituting the heat-resistant resin layer 3B preferably has a heat of crystal fusion of 20 J / g or more and 100 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JIS K7221. It is more preferably 25 J / g or more and 65 J / g or less, more preferably 25 J / g or more and 55 J / g or less, more preferably 28 J / g or more and 50 J / g or less, and more preferably 28 J / g g or more and 40 J / g or less is more preferable, and 28 J / g or more and 35 J / g or less is more preferable. When it is 20 J / g or more, it is possible to effectively exhibit heat resistance and releasability that can withstand hot press molding in a resin sealing process and the like, and the dimensional change rate can be slightly suppressed. The occurrence of wrinkles can also be prevented. On the other hand, since the crystal heat of fusion is 100 J / g or less, the heat resistant resin layer 3B can be provided with an appropriate hardness, so that sufficient followability of the film to the mold is ensured in the resin sealing step and the like. In addition to being able to do so, there is no risk of the film being easily damaged. In the present embodiment, the crystal melting calorie is the calorific value (J / g) on the vertical axis obtained in the first heating step in the differential scanning calorimetry (DSC) measurement according to JISK7221 and the horizontal axis. In the chart showing the relationship with temperature (° C.), it is a numerical value obtained by the sum of peak areas having a peak at 120 ° C. or higher.
The amount of heat of crystal fusion of the heat-resistant resin layer 3B can be adjusted by appropriately setting the heating and cooling conditions during film production and the stretching conditions.

The thickness of the heat-resistant resin layer 3B is not particularly limited as long as the film strength can be secured, but is usually 1 to 1
It is 00 μm, preferably 5 to 50 μm.

Other layers The release film for a process of the third invention of the present application has layers other than the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ as long as it does not contradict the purpose of the third invention of the present application. May be. For example, an adhesive layer may be provided between the release layer 3A (or the release layer 3A ′) and the heat resistant resin layer 3B as necessary. The material used for the adhesive layer is not particularly limited as long as it can firmly bond the release layer 3A and the heat-resistant resin layer 3B and does not peel in the resin sealing step or the release step.

For example, when the release layer 3A (or release layer 3A ′) contains 4-methyl-1-pentene copolymer, the adhesive layer is modified 4-methyl-1 graft-modified with an unsaturated carboxylic acid or the like. It is preferably a pentene copolymer resin, an olefin adhesive resin composed of a 4-methyl-1-pentene copolymer and an α-olefin copolymer. When the release layer 3A (or the release layer 3A ') contains a fluororesin, the adhesive layer is preferably a pressure-sensitive adhesive such as polyester, acrylic, or fluororubber. The thickness of the adhesive layer is not particularly limited as long as the adhesiveness between the release layer 3A (or the release layer 3A ') and the heat-resistant resin layer 3B can be improved, but is 0.5 to 10 μm, for example.

The total thickness of the process release film of the third invention of the present application is not particularly limited, but is preferably 10 to 300 μm, for example, and more preferably 30 to 150 μm. When the total thickness of the release film is in the above range, it is preferable because the handling property when used as a roll is good and the amount of discarded film is small.

Hereinafter, preferred embodiments of the process release film of the third invention of the present application will be described in more detail. FIG. 1 is a schematic diagram showing an example of a three-layer process release film. As shown in FIG. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one surface of the release film 16 with an adhesive layer 14 interposed therebetween.

The release layer 16 is the aforementioned release layer 3A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer 3B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing process; the heat-resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the mold in the sealing process.

FIG. 2 is a schematic diagram showing an example of a five-layer process release film. Members having the same functions as those in FIG. 1 are denoted by the same reference numerals. As shown in FIG. 2, the release film 20 includes a heat resistant resin layer 12 and a release layer 16 A and a release layer 16 B formed on both surfaces of the release film 16 via an adhesive layer 14. The release layer 16A is the aforementioned release layer 3A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer 3B, the release layer 16B is the aforementioned release layer 3A ', and the adhesive layer 14 is the aforementioned It is an adhesive layer.

The compositions of the release layers 16A and 16B may be the same as or different from each other. The thicknesses of the release layers 16A and 16B may be the same as or different from each other. However, it is preferable that the release layers 16A and 16B have the same composition and thickness as each other because a symmetric structure is obtained and the release film itself is hardly warped. In particular, since the release film of the third invention of the present application may be stressed by heating in the sealing process, it is preferable to suppress warping. As described above, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good release properties can be obtained on both the molded product and the inner surface of the mold.

Process Release Film Manufacturing Method The process release film of the third invention of the present application can be manufactured by any method. For example, 1) a method for producing a release film for a process by coextruding and laminating a release layer 3A and a heat resistant resin layer 3B (coextrusion forming method), and 2) on a film to be a heat resistant resin layer 3B In addition, the molten resin of the resin to be the release layer 3A and the adhesive layer is applied and dried, or the resin solution in which the resin to be the release layer 3A and the adhesive layer is dissolved in a solvent is applied and dried. Process for producing release film for process (coating method), 3) A film to be the release layer 3A and a film to be the heat-resistant resin layer 3B are produced in advance, and these films are laminated (laminated). Thus, there is a method for producing a release film for a process (lamination method).

1) The coextrusion molding method is preferable in that a defect due to a foreign matter biting between the resin layer to be the release layer 3A and the resin layer to be the heat-resistant resin layer 3B or a warp of the release film is difficult to occur. . 3) The laminating method is a manufacturing method suitable when a stretched film is used for the heat resistant resin layer 3B. In this case, it is preferable to form an appropriate adhesive layer at the interface between the films as necessary. In order to improve the adhesiveness between the films, a surface treatment such as a corona discharge treatment may be applied to the interface between the films as necessary.

Manufacturing process The release film for a process of the third invention of the present application is used by placing a semiconductor chip or the like in a mold and injecting and molding a resin between the semiconductor chip and the inner surface of the mold. Can do. By using the process release film of the third invention of the present application, it is possible to effectively prevent mold release failure from the mold, generation of burrs, and the like.
The resin used in the manufacturing process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the technical field, and in particular, epoxy-based thermosetting resins are used. It is preferable to use it.
As the above manufacturing process, sealing of a semiconductor chip is most representative, but it is not limited to this, and the third invention of the present application is also applicable to a fiber reinforced plastic molding process, a plastic lens molding process, etc. Can do.

3, 4A and 4B are schematic views showing an example of a method for producing a resin-encapsulated semiconductor using the release film of the third invention of the present application.
As shown in FIG. 3a, the release film 1 of the third invention of the present application is supplied from the roll-shaped roll into the molding die 2 by the roll 1-2 and the roll 1-3. Next, the release film 1 is disposed on the inner surface of the upper mold 2. If necessary, the inner surface of the upper mold 2 may be evacuated to bring the release film 1 into close contact with the inner surface of the upper mold 2. A semiconductor chip 6 disposed on a substrate is disposed in a lower mold 5 of the molding apparatus, and a sealing resin is disposed on the semiconductor chip 6 or a liquid sealing resin so as to cover the semiconductor chip 6. The sealing resin 4 is accommodated between the upper mold 2 and the lower mold 5 on which the release film 1 that has been sucked and adhered is exhausted. Next, as shown in FIG. 3b, the upper mold 2 and the lower mold 5 are closed through the release film 1 of the third invention of the present application, and the sealing resin 4 is cured.

As shown in FIG. 3 c, the sealing resin 4 流動 flows into the mold by mold closing and curing, and the sealing resin 4 流入 flows into the space and fills and surrounds the side surface of the semiconductor chip 6. The chip 6 is taken out by the upper mold 2 and the lower mold 5 being opened. After the mold is opened and the molded product is taken out, the release film 1 is repeatedly used for a plurality of times or a new release film is supplied and subjected to the next resin molding.

The release film of the third invention of the present application is adhered to the upper mold, interposed between the mold and the sealing resin, and resin molding prevents the resin from adhering to the mold. The molded product can be easily released from the mold.
The release film can be newly supplied and resin-molded for each resin molding operation, or can be newly supplied and resin-molded for each of a plurality of resin molding operations.

Thus, since the release film 1 has the release layer 3A (and the release layer 3A 'if necessary) having a high release property, the semiconductor package 4-2 can be easily released. Moreover, since the release film 1 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 8 while having excellent followability to the mold shape. For this reason, a sealed semiconductor package having a good external appearance can be obtained without generating wrinkles on the resin-sealed surface of the sealed semiconductor package 4-2 or generating a portion not filled with resin (resin chipping). 4-2 can be obtained.

Further, not only the compression molding method in which the solid sealing resin material 4 is pressurized and heated as shown in FIG. 3, but also a transfer molding method in which a sealing resin material in a fluid state is injected as described later. Also good.

4A and 4B are schematic views showing a transfer mold method which is an example of a method for producing a resin-encapsulated semiconductor using the release film of the third invention of the present application.

As shown in FIG. 4A, the release film 22 of the third invention of the present application is supplied from the roll-shaped roll into the molding die 28 by the roll 24 and the roll 26 (step a). Next, the release film 22 is disposed on the inner surface 30A of the upper mold 30 (step b). If necessary, the upper mold inner surface 30A may be evacuated to bring the release film 22 into close contact with the upper mold inner surface 30A. Next, the semiconductor chip 34 to be resin-sealed (semiconductor chip 34 fixed to the substrate 34A) is placed in the molding die 28, and the sealing resin material 36 is set (step c), and the mold is clamped ( Step d).

Thus, since the release film 22 has the release layer 3A (and the release layer 3A 'if necessary) having a high release property, the semiconductor package 40 can be easily released. Moreover, since the release film 22 has moderate flexibility, it is less likely to become wrinkles due to the heat of the molding die 28 while having excellent followability to the die shape. Therefore, it is possible to obtain the semiconductor package 40 having a good appearance without transferring wrinkles on the resin sealing surface of the semiconductor package 40 or generating a portion not filled with resin (resin chipping).

The release film of the third invention of the present application is not limited to the step of resin-sealing a semiconductor element, but a step of molding and releasing various molded products using a molding die, for example, fiber reinforced plastic molding and release step, plastic It can also be preferably used in lens molding and mold release processes.

Process Release Film The process release film of the fourth invention of the present application includes the following four aspects.
(Aspect 4-1)
A release film for process which is a laminated film including a release layer 4A and a heat resistant resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
(Aspect 4-2)
A release film for process which is a laminated film including a release layer 4A and a heat resistant resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
(4-3 embodiment)
A release film for process which is a laminated film including a release layer 4A, a heat-resistant resin layer 4B, and a release layer 4A ′ in this order,
The contact angle of the release layer 4A and the release layer 4A ′ with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
(Aspect 4-4)
A release film for process which is a laminated film including a release layer 4A, a heat-resistant resin layer 4B, and a release layer 4A ′ in this order,
The contact angle of the release layer 4A and the release layer 4A ′ with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.

As is clear from the above embodiments, the release film for process of the fourth invention of the present application (hereinafter also simply referred to as “release film”) has a release layer 4A having release properties for molded products and molds, and A laminated film including a release layer 4A ′ and a heat-resistant resin layer 4B that supports the release layer as desired, wherein the heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent. .

The process release film of the fourth invention of the present application is disposed on the inner surface of a molding die when a semiconductor element or the like is resin-sealed inside the molding die. At this time, the release layer 4A of the release film (or the release layer 4A ′ if the release layer 4A ′ is present) may be placed on the resin-encapsulated semiconductor element or the like (molded product) side. It is preferable to arrange. By disposing the release film of the fourth invention of the present application, it is possible to easily release the resin-encapsulated semiconductor element and the like from the mold.
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °. By having such a contact angle, the release layer 4A has low wettability and is fixed to the cured sealing resin or the mold surface. Without this, the molded product can be easily released.
The contact angle of the release layer 4A with respect to water is preferably 95 ° to 120 °, more preferably 98 ° to 115 °, and still more preferably 100 ° to 110 °.

As described above, since the release layer 4A (in some cases, the release layer 4A ′) is disposed on the molded product side, from the viewpoint of the appearance of the molded product, the release layer 4A in the resin sealing process (in some cases, the release layer 4A ′). It is preferable to suppress the generation of wrinkles in the mold layer 4A ′). This is because if wrinkles are generated in the release layer 4A (in some cases, the release layer 4A '), the generated wrinkles are transferred to the molded product, and there is a high possibility that an appearance defect of the molded product will occur.

In the fourth invention of the present application, in order to achieve the above-mentioned object, as the laminated film constituting the process release film, the release layer 4A (and the release layer 4A ′ if necessary) and the release layer are supported. A laminated film including the heat-resistant resin layer 4B, wherein a laminated film having a specific value of the tensile elastic modulus is used, and the heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent. . Here, the laminated film including the release layer 4A (and optionally the release layer 4A ′) and the heat-resistant resin layer 4B that supports the release layer has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa. Or the tensile elastic modulus at 170 ° C. is 75 MPa to 500 MPa.
Mechanism in which appearance defects of molded products are extremely effectively suppressed by combining a laminated film having the above-mentioned specific value with a tensile elastic modulus and a heat-resistant resin layer including a layer containing a polymeric antistatic agent Although it is not always clear, to suppress the generation of wrinkles due to the tensile modulus of the laminated film being the above specific value, to the suppression of static electricity and to the process by having a layer containing a polymeric antistatic agent It is presumed that the suppression of the uptake of foreign matters such as powders exhibits some synergistic effect. That is, since foreign substances such as powder can be the starting point of soot, by suppressing the uptake of foreign substances, the suppression of soot generation becomes more effective, while the soot can be the aggregation point of foreign substances. By suppressing the occurrence of the occurrence, the agglomeration and growth of foreign substances are more effectively suppressed, which has some relationship with the suppression of the appearance defect of the molded product at a high level that could not be predicted by the prior art. Presumed.
In addition, the surface specific resistance value in the release layer 4A (and release layer 4A ′ if necessary) of the laminated film is preferably 1 × 10 ¹³ Ω / □ or less from the viewpoint of preventing adhesion of dust and the like in the semiconductor manufacturing process. More preferably, it is 5 × 10 ¹² Ω / □ or less, more preferably 1 × ¹² Ω / □ or less, and particularly preferably 5 × 10 ¹¹ Ω / □ or less.
The surface specific resistance value in the release layer 4A (and optionally the release layer 4A ′) of the laminated film can be measured by, for example, the method described in Examples of the present application.

As described above, the laminated film including the release layer 4A (and optionally the release layer 4A ′) and the heat-resistant resin layer 4B that supports the release layer has a tensile elastic modulus at 120 ° C. of 75 MPa. 500 MPa, or its tensile elastic modulus at 170 ° C. is 75 MPa to 500 MPa. Furthermore, the laminated film preferably has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa, and a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
When the tensile elastic modulus at 120 ° C. of the laminated film is from 75 MPa to 500 MPa, or the tensile elastic modulus at 170 ° C. is from 75 MPa to 500 MPa, generation of wrinkles in the release layer in the resin sealing process or the like It can be effectively suppressed. The mechanism by which the generation of wrinkles in the release layer is suppressed when the tensile modulus at a specific temperature of the laminated film constituting the release film for the process exhibits the above specific value is not necessarily clear, but it is heated during the process. It has a tensile modulus of elasticity above a certain value in a state where it has been suppressed, and deformation that leads to generation of wrinkles is suppressed, and having a tensile modulus of elasticity below a certain value is related to the dispersion of strain It is guessed. If it exceeds 500 MPa, the mold followability is inferior, so that it is difficult to fill the sealing resin at the end portion, and there is a high possibility of appearance defects such as occurrence of resin chipping.

The laminated film constituting the process release film of the fourth invention of the present application preferably has a tensile elastic modulus at 120 ° C. of 80 MPa to 400 MPa,
More preferably from 85 MPa to 350 MPa,
More preferably, it is 88 MPa to 300 MPa,
It is particularly preferable that the pressure is 90 MPa to 280 MPa.
The laminated film constituting the process release film of the fourth invention of the present application preferably has a tensile elastic modulus at 170 ° C. of 80 MPa to 400 MPa,
More preferably from 85 MPa to 350 MPa,
More preferably from 88 MPa to 300 MPa, more preferably from 90 MPa to 280 MPa, still more preferably from 95 MPa to 200 MPa,
It is particularly preferable that the pressure is 105 MPa to 170 MPa.
The laminated film constituting the process release film of the fourth invention of the present application is free during processing that the tensile elastic modulus at 120 ° C. and the tensile elastic modulus at 170 ° C. are both within the above preferred range. It is particularly preferred because of its wide range of uses and applications.

In addition, the laminated film including the release layer 4A (and the release layer 4A ′ if necessary) and the heat-resistant resin layer 4B that supports the release layer is from 23 ° C. to 120 ° C. in the TD direction (lateral direction). It is preferable that the thermal dimensional change rate is 3% or less, or the thermal dimensional change rate from 23 ° C. to 170 ° C. in the TD direction (lateral direction) is 4% or less. Further, the laminated film has a thermal dimensional change rate of 23% to 120 ° C. in the TD direction (lateral direction) of 3% or less and a thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The rate is more preferably 4% or less.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) of the laminated film is 3% or less, or the thermal dimensional change from 23 ° C. to 170 ° C. in the TD direction (lateral direction). When the rate is 4% or less, generation of wrinkles in the release layer in the resin sealing step or the like can be further effectively suppressed. In this embodiment, as the laminated film constituting the process release film, the film having a specific rate of thermal dimensional change in the transverse (TD) direction described above is used to further effectively suppress generation of wrinkles in the release layer. Although the mechanism of the release layer 4A (or the release layer 4A ′) due to heating / cooling during the process can be reduced by using a laminated film having a relatively small thermal expansion / shrinkage. It is presumed to be related to being suppressed.

The process release film of the fourth invention of the present application, which is a laminated film including the release layer 4A (and the release layer 4A ′ if necessary) and the heat-resistant resin layer 4B that supports the release layer, has a TD direction ( It is preferable that the sum of the thermal dimensional change rate in the horizontal direction and the thermal dimensional change rate in the MD direction (longitudinal direction at the time of manufacturing the film; hereinafter also referred to as “longitudinal (MD) direction”) is not more than a specific value.
That is, the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the laminated film is 6% or less. On the other hand, the laminated film is the sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the TD direction (lateral direction) and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the vertical (MD) direction. Is preferably −5.0% or more.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. in the transverse (TD) direction and the longitudinal (MD) direction of the laminated film including the release layer 4A (and the release layer 4A ′ if necessary) and the heat-resistant resin layer 4B. When the sum of the thermal dimensional change rates from 23 ° C. to 120 ° C. is 6% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.

Further, the rate of thermal dimensional change from 23 ° C. to 170 ° C. in the transverse (TD) direction and longitudinal (MD) of the laminated film including the release layer 4A (and the release layer 4A ′ if necessary) and the heat-resistant resin layer 4B. The sum of the thermal dimensional change rates from 23 ° C. to 170 ° C. in the direction is preferably 7% or less, while the laminated film has a thermal dimension from 23 ° C. to 170 ° C. in the TD direction (lateral direction). The sum of the rate of change and the rate of change in the thermal dimension from 23 ° C. to 170 ° C. in the machine direction (MD) is preferably −5.0% or more.
By the sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the laminated film and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction being 7% or less, Generation of wrinkles when mounted on the inner surface of the mold can be further effectively suppressed.

Release layer 4A
The release layer 4A constituting the process release film of the fourth invention of the present application has a water contact angle of 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98 ° to 115. °, more preferably 100 ° to 110 °. In view of excellent mold releasability and availability, it is preferable to include a resin selected from the group consisting of a fluororesin, 4-methyl-1-pentene (co) polymer, and a polystyrene resin.

The fluororesin that can be used for the release layer 4A is the same as that described for the release layer 3A.
The 4-methyl-1-pentene (co) polymer that can be used for the release layer 4A is the same as that described for the release layer 3A.
Furthermore, the polystyrene resin that can be used for the release layer 4A is the same as that described for the release layer 3A.

The release layer 4A preferably has heat resistance that can withstand the mold temperature during molding (typically 120 to 180 ° C.). From this point of view, the release layer 4A preferably includes a crystalline resin having a crystal component, and the melting point of the crystalline resin is preferably 190 ° C. or higher, and more preferably 200 ° C. or higher and 300 ° C. or lower.
In order to provide crystallinity to the release layer 4A, for example, a fluororesin preferably contains at least a structural unit derived from tetrafluoroethylene, and a 4-methyl-1-pentene (co) polymer has 4-methyl-1 -It preferably contains at least a structural unit derived from pentene, and in a polystyrene resin, it preferably contains at least syndiotactic polystyrene. By including a crystal component in the resin constituting the release layer 4A, it is difficult for wrinkles to occur in the resin sealing step and the like, and it is suitable for suppressing wrinkles from being transferred to a molded product to cause poor appearance. .

The resin containing the crystalline component constituting the release layer 4A has a heat of crystal melting of 15 J / g or more and 60 J / g or less in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221. It is preferable that it is 20 J / g or more and 50 J / g or less. When it is 15 J / g or more, in addition to being able to more effectively express heat resistance and releasability that can withstand hot press molding in the resin sealing step, etc., it also suppresses the dimensional change rate. Therefore, generation of wrinkles can be prevented. On the other hand, if the heat of crystal fusion is 60 J / g or less, the release layer 4A has an appropriate hardness, so that sufficient followability to the mold of the film can be obtained in the resin sealing step or the like. There is no risk of film damage.

The release layer 4A may further contain other resins in addition to the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin. In this case, other resins and their contents are the same as those described for the release layer 3A.

In addition to the fluororesin, 4-methyl-1-pentene (co) polymer, and / or polystyrene resin, the release layer 4A includes a heat resistance stabilizer, weather resistance, and the like as long as the object of the fourth invention of the present application is not impaired. You may also contain the well-known additive generally mix | blended with resin for films, such as a stabilizer, a rust prevention agent, a copper-resistant damage stabilizer, and an antistatic agent. The content of these additives can be, for example, 0.0001 to 10 parts by weight with respect to 100 parts by weight of the fluororesin, 4-methyl-1-pentene copolymer, and / or polystyrene resin.

The thickness of the release layer 4A is not particularly limited as long as the release property for the molded product is sufficient, but is usually 1 to 50 μm, preferably 5 to 30 μm.

The surface of the release layer 4A may have a concavo-convex shape as necessary, thereby improving the releasability. The method for imparting irregularities to the surface of the release layer 4A is not particularly limited, but a general method such as embossing can be employed.

Release layer 4A '
The process release film of the fourth invention of the present application may further include a release layer 4A ′ in addition to the release layer 4A and the heat-resistant resin layer 4B. That is, the process release film of the fourth invention of the present application is a process release film that is a laminated film including the release layer 4A, the heat-resistant resin layer 4B, and the release layer 4A ′ in this order. Good.
The contact angle with respect to water of the release layer 4A ′ that may constitute the process release film of the fourth invention of the present application is 90 ° to 130 °, preferably 95 ° to 120 °, more preferably 98. It is from ° to 115 °, more preferably from 100 ° to 110 °. The preferable material, configuration, physical properties, and the like of the release layer 4A ′ are the same as those described above for the release layer 4A.

The release layer 4A and the release layer 4A ′ are the same when the release film for process is a laminated film including the release layer 4A, the heat-resistant resin layer 4B, and the release layer 4A ′ in this order. It may be a layer having a different structure or a layer having a different structure.
From the standpoints of warpage prevention and ease of handling due to the same releasability on both surfaces, the release layer 4A and the release layer 4A ′ may have the same or substantially the same configuration. Preferably, from the viewpoint of optimally designing each in relation to the process using the release layer 4A and the release layer 4A ′, for example, the release layer 4A has excellent release properties from the mold. From the viewpoint of making the layer 4A ′ excellent in releasability from the molded product, it is preferable that the release layer 4A and the release layer 4A ′ have different configurations.
When the release layer 4A and the release layer 4A ′ have different configurations, the release layer 4A and the release layer 4A ′ may be made of the same material and have different configurations such as thickness. However, the materials and other configurations may be different.

Heat resistant resin layer 4B
The heat-resistant resin layer 4B constituting the process release film of the fourth invention of the present application has a function of supporting the release layer 4A (and possibly the release layer 4A ') and suppressing wrinkles due to mold temperature and the like. Have.
The heat-resistant resin layer 4B constituting the process release film of the fourth invention of the present application includes a layer 4B1 containing a polymeric antistatic agent. Here, “including” the layer 4B1 containing the polymeric antistatic agent means that the entire heat resistant resin layer 4B is composed of the layer 4B1 containing the polymeric antistatic agent, and the heat resistant resin layer. When a part of 4B is composed of a layer 4B1 containing a polymer antistatic agent, it is used to include both. Therefore, the heat-resistant resin layer 4B may or may not further include a layer other than the layer 4B1 containing the polymer antistatic agent.

The heat-resistant resin layer 4B constituting the process release film of the fourth invention of the present application includes a layer 4B1 containing a high-molecular antistatic agent, and thus has a low surface resistivity and contributes to antistatic.
The surface resistivity of the heat-resistant resin layer 4B is preferably 10 ¹⁰ Ω / □ or less, preferably 10 ⁹ Ω / □ or less, from the viewpoint of preventing dust and the like from adhering to the release layer 4A of the laminated film of the fourth invention of the present application. Particularly preferred. When the surface specific resistance value is 10 ¹⁰ Ω / □ or less, the antistatic property is effectively expressed also on the surface of the release film for process of the present invention. Therefore, the adhesion of foreign matters such as dust due to static electricity can be effectively suppressed, and even when a part of a semiconductor element is in direct contact with the process release film, for example, when manufacturing a semiconductor package, the process release film The destruction of the semiconductor element due to charging-discharging can be effectively suppressed.
The surface specific resistance value of the heat-resistant resin layer 4B is preferably as low as possible from the viewpoint of preventing adhesion of dust and the like to the release layer 4A of the laminated film of the fourth invention of the present application, and the lower limit is not particularly limited. The surface specific resistance value of the heat resistant resin layer 4B tends to decrease as the conductive performance of the polymer antistatic agent increases and as the content of the polymer antistatic agent increases.
The surface specific resistance value of the heat-resistant resin layer 4B can be measured by, for example, the method described in the examples of the present application. However, the heat-resistant resin layer 4B before lamination is used as a sample.

As another layer other than the layer 4B1 containing the polymer antistatic agent, for example, an adhesive layer 4B2 containing an adhesive can be preferably used. That is, the heat resistant resin layer 4B may include a layer 4B1 containing a polymer antistatic agent and an adhesive layer 4B2 containing an adhesive.
In this case, the heat-resistant resin layer 4B may be composed of only the layer 4B1 containing a polymer antistatic agent and the adhesive layer 4B2 containing an adhesive, or a layer containing a polymer antistatic agent. Other layers other than 4B1 and the adhesive layer 4B2 containing an adhesive, for example, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas barrier layer, and the like may be further included.

Further, the layer 4B1 containing a polymer antistatic agent may also contain an adhesive. That is, the heat resistant resin layer 4B may include a layer 4B3 containing a polymer antistatic agent and an adhesive.
In this case, the heat-resistant resin layer 4B may be composed only of the layer 4B3 containing the polymer antistatic agent and the adhesive, or other than the layer 4B3 containing the polymer antistatic agent and the adhesive. Other layers, for example, a layer 4B1 containing a polymer antistatic agent, an adhesive layer 4B2 containing an adhesive, a layer of a thermoplastic resin not containing an antistatic agent and an adhesive, a gas barrier layer, and the like may further be included. .

In the release film for process according to the fourth invention of the present application, the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B is 3% or less, or the transverse direction of the heat resistant resin layer 4B. It is preferable that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the (TD) direction is 3% or less. Further, the heat-resistant resin layer 4B has a thermal dimensional change rate of 23% to 120 ° C. in the transverse (TD) direction of 3% or less and a thermal dimension from 23 ° C. to 170 ° C. in the transverse (TD) direction. The change rate is more preferably 3% or less.
The heat dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B is 3% or less, or the heat from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B. When the dimensional change rate is 3% or less, generation of wrinkles when mounted on the inner surface of the mold can be more effectively suppressed.
As the heat-resistant resin layer 4B, the mechanism by which the generation of wrinkles in the release layer is more effectively suppressed by using a resin layer in which the rate of thermal dimensional change in the transverse (TD) direction exhibits the above specific value is not necessarily clear. However, the thermal expansion / contraction of the release layer 4A (or the release layer 4A ′) due to heating / cooling during the process is suppressed by using the heat-resistant resin layer 4B having relatively small thermal expansion / contraction. It is presumed to be related.

Although any resin layer including an unstretched film can be used for the heat-resistant resin layer 4B, it is particularly preferable to comprise a stretched film.
The stretched film tends to have a low or negative coefficient of thermal expansion due to the influence of stretching in the manufacturing process, and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction is 3% or less. Alternatively, since it is relatively easy to realize the characteristic that the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B is 3% or less, the heat resistant resin layer 4B It can be preferably used.
The thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.
The thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B is preferably 2% or less, more preferably 1.5% or less, and 1% or less. More preferably, it is preferably -10% or more.

In the release film for process according to the fourth invention of the present application, the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat-resistant resin layer 4B and the heat from 23 ° C. to 120 ° C. in the longitudinal (MD) direction. The sum of the dimensional change rates is 6% or less, or the thermal dimensional change rate in the transverse (TD) direction from 23 ° C. to 170 ° C. and the longitudinal (MD) direction from 23 ° C. to 170 ° C. The sum of the thermal dimensional change rates is preferably 5% or less. The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction is 6% or less, and The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 4B is 5% or less. Is more preferable. When the sum of the thermal dimensional change rate in the transverse (TD) direction and the thermal dimensional change rate in the longitudinal (MD) direction of the heat-resistant resin layer 4B is in the above range, generation of wrinkles when mounted on the inner surface of the mold is further increased. It can be effectively suppressed.
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the vertical (MD) direction is −3.0% or more. It is more preferably 5.0% or less, and further preferably -2.0% or more and 4.5% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction of the heat resistant resin layer 4B and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the vertical (MD) direction is −15.5% or more. It is more preferably 5.0% or less, and further preferably -10.0% or more and 4.5% or less.
From the viewpoint of keeping the sum of the thermal dimensional change rate in the transverse (TD) direction and the thermal dimensional change rate in the longitudinal (MD) direction of the heat-resistant resin layer 4B within the above range, it is advantageous to use a stretched film. It is particularly advantageous to control the conditions appropriately.

Details of the stretched film are the same as those described for the heat-resistant resin layer 3B.

The heat-resistant resin layer 4B has heat resistance that can withstand the mold temperature (typically 120 to 180 ° C.) at the time of molding from the viewpoint of controlling the strength of the film and the rate of thermal dimensional change within an appropriate range. It is preferable. From this viewpoint, the heat-resistant resin layer 4B preferably includes a crystalline resin having a crystalline component, and the melting point of the crystalline resin is preferably 125 ° C. or higher, and the melting point is 155 ° C. or higher and 300 ° C. or lower. Is more preferably 185 to 210 ° C., and particularly preferably 185 to 205 ° C.

As described above, the heat resistant resin layer 4B preferably contains a crystalline resin having a crystalline component. As a crystalline resin to be contained in the heat resistant resin layer 4B, for example, a crystalline resin such as a polyester resin, a polyamide resin, or a polypropylene resin can be used for a part or all thereof. Specifically, it is preferable to use polyethylene terephthalate or polybutylene terephthalate for the polyester resin, polyamide 6 or polyamide 66 for the polyamide resin, and isotactic polypropylene for the polypropylene resin.

By including the crystalline component of the crystalline resin in the heat-resistant resin layer 4B, it is difficult to generate wrinkles in the resin sealing process and the like, and it is more advantageous to suppress the wrinkles from being transferred to the molded product and causing poor appearance. Become.
The resin constituting the heat-resistant resin layer 4B preferably has a heat of crystal melting in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of 20 J / g or more and 100 J / g or less. It is more preferably 25 J / g or more and 65 J / g or less, more preferably 25 J / g or more and 55 J / g or less, more preferably 28 J / g or more and 50 J / g or less, and more preferably 28 J / g g or more and 40 J / g or less is more preferable, and 28 J / g or more and 35 J / g or less is more preferable. When it is 20 J / g or more, it is possible to effectively exhibit heat resistance and releasability that can withstand hot press molding in a resin sealing process and the like, and the dimensional change rate can be slightly suppressed. The occurrence of wrinkles can also be prevented. On the other hand, since the heat of crystal melting is 100 J / g or less, the heat resistant resin layer 4B can be provided with an appropriate hardness, so that sufficient followability of the film to the mold is ensured in the resin sealing step and the like. In addition to being able to do so, there is no risk of the film being easily damaged. In the present embodiment, the crystal melting calorie is the calorific value (J / g) on the vertical axis obtained in the first heating step in the differential scanning calorimetry (DSC) measurement according to JISK7221 and the horizontal axis. In the chart showing the relationship with temperature (° C.), it is a numerical value obtained by the sum of peak areas having a peak at 120 ° C. or higher.
The heat of crystal fusion of the heat-resistant resin layer 4B can be adjusted by appropriately setting the heating and cooling conditions and the stretching conditions during film production.

The thickness of the heat-resistant resin layer 4B is not particularly limited as long as the film strength can be ensured, but usually 1 to 1
It is 00 μm, preferably 5 to 50 μm.

Layer 4B1 containing a polymeric antistatic agent
It is known that the polymer antistatic agent in the layer 4B1 containing the polymer antistatic agent that is suitably used in the heat resistant resin layer 4B constituting the laminate of the fourth invention of the present application has an antistatic function. The high molecular compound which can be used can be used. For example, a cationic copolymer having a quaternary ammonium base in the side group, an anionic compound containing polystyrene sulfonic acid, a compound having a polyalkylene oxide chain (a polyethylene oxide chain or a polypropylene oxide chain is preferred), a polyethylene glycol methacrylate copolymer. Examples thereof include nonionic polymers such as polymers, polyether ester amides, polyether amide imides, polyether esters, ethylene oxide-epichlorohydrin copolymers, and π-conjugated conductive polymers. These may be used alone or in combination of two or more.

The quaternary ammonium base in the copolymer having a quaternary ammonium base in the side group has an effect of imparting dielectric polarization and rapid dielectric polarization relaxation due to conductivity.
The copolymer preferably has a carboxy group together with a quaternary ammonium base in the side group. When it has a carboxy group, the copolymer has crosslinkability and can form the layer 4B1 alone. Further, when used in combination with an adhesive such as a urethane-based adhesive, it reacts with the adhesive to form a crosslinked structure, and the adhesiveness, durability, and other mechanical properties can be significantly improved.
The copolymer may further have a hydroxy group as a side group. The hydroxy group has an effect of increasing adhesiveness by reacting with a functional group in the adhesive such as an isocyanate group.

As the polymer antistatic agent, one produced by a known method may be used, or a commercially available one may be used. For example, as a commercial product of a copolymer having a quaternary ammonium base and a carboxy group in the side group, “BONDEIP (trade name) -PA100 main agent” manufactured by Konishi Co., Ltd. and the like can be mentioned.

Preferable embodiments of the layer 4B1 containing the polymer antistatic agent include the following layers (1) to (4).
Layer (1): The polymer antistatic agent itself has a film-forming ability, and the polymer antistatic agent is applied as it is or dissolved in a solvent and wet-coated, and dried if necessary. Layer.
Layer (2): A layer formed by melt-coating the polymer antistatic agent, wherein the polymer antistatic agent itself has film-forming ability and can be melted.
Layer (3): The binder has film-forming ability and can be melted, and is formed by melt-coating a composition in which a polymer antistatic agent is dispersed or dissolved in the binder. Layer.
Layer (4): The binder has film-forming ability, and the composition containing the binder and the polymeric antistatic agent is applied as it is or dissolved in a solvent, and wet-coated, and dried if necessary. Layer formed. However, what corresponds to layer (1) shall not correspond to layer (4).

In the layer (1), the polymer antistatic agent itself has film-forming ability means that the polymer antistatic agent is soluble in a solvent such as an organic solvent, and the solution is applied wet and dried. This means that a film is formed.
In the layer (2), the fact that the polymer antistatic agent itself can be melted means that it is melted by heating. The terms “having film-forming ability” and “fusible” for the binder in layers (3) and (4) have the same meaning.

A general-purpose thermoplastic resin is mentioned as a binder in a layer (3). The thermoplastic resin is preferably a resin having a functional group contributing to adhesion so as to adhere at the time of melt molding. Examples of the functional group include a carbonyl group.
The content of the polymer antistatic agent in the layer (3) is preferably 10 to 40 parts by weight, particularly preferably 10 to 30 parts by weight, based on the total weight of the layer (3). The preferable range of the thickness of the layer (3) is the same as the preferable range of the thickness of the layer (1).

One example of a composition that forms layer (4) is an adhesive. The adhesive means a material containing a main agent and a curing agent, which is cured by heating or the like and exhibits adhesiveness.
At this time, the layer 4B1 containing the polymer antistatic agent also corresponds to the layer 4B3 containing the polymer antistatic agent and the adhesive.
The adhesive may be a one-component adhesive or a two-component adhesive.
As an adhesive for forming the layer (4) (hereinafter also referred to as an adhesive for forming the layer (4)), for example, a polymer antistatic agent is added to an adhesive not containing a polymer antistatic agent. And the like.
The polymer antistatic agent added to the adhesive may have a film forming ability or may not have a film forming ability (for example, a π-conjugated conductive polymer).
As the adhesive that does not contain a polymer antistatic agent, those known as adhesives for dry lamination can be used. For example, polyvinyl acetate adhesive; homopolymer or copolymer of acrylic acid ester (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or acrylic acid ester and other monomers (methacrylic acid) Polyacrylate adhesives consisting of copolymers with methyl, acrylonitrile, styrene, etc .; Cyanoacrylate adhesives; Ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic acid) Etc.) Ethylene copolymer adhesives made of copolymers, etc .; Cellulose adhesives; Polyester adhesives; Polyamide adhesives; Polyimide adhesives; Amino resin systems made of urea resins or melamine resins Adhesive; phenolic resin adhesive; epoxy adhesive; polyol (polyether polyol) Polyurethane adhesive that crosslinks with isocyanate and / or isocyanurate; reactive (meth) acrylic adhesive; rubber adhesive composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc .; silicone Adhesives such as inorganic adhesives made of alkali metal silicate, low-melting glass, etc .; other adhesives can be used.

The content of the polymer antistatic agent in the layer (4) forming adhesive is preferably such that the surface specific resistance value of the layer (4) is 10 ¹⁰ Ω / □ or less, preferably 10 ⁹ Ω / □ or less. Particularly preferred.
From the viewpoint of antistatic, the higher the content of the polymeric antistatic agent in the layer (4) forming adhesive, the better. However, the polymeric antistatic agent is a π-conjugated conductive polymer, When the layer 4B1 is formed using an adhesive containing no molecular antistatic agent and a π-conjugated conductive polymer added as an adhesive for forming the layer (4), the content of the high molecular antistatic agent When the amount increases, the adhesiveness of the layer (4) decreases, and the adhesion between the first thermoplastic resin layer 2 and the second thermoplastic resin layer 3 may be insufficient. Therefore, the content of the polymer antistatic agent in the layer (4) forming adhesive in this case is preferably 40% by mass or less, and preferably 30% by mass or less, based on the solid content of the resin serving as the binder. Is particularly preferred. The lower limit is preferably 1% by mass, particularly preferably 5% by mass.

The thickness of the layer (4) is preferably 0.2 to 5 μm, particularly preferably 0.5 to 2 μm. When the thickness of the layer (4) is not less than the lower limit of the above range, the adhesion between the first thermoplastic resin layer and the second thermoplastic resin layer is excellent, and the antistatic property is excellent. It is excellent in productivity as it is below the upper limit of the said range.

The polymer antistatic layer of the layer 4B1 may be one layer or two or more layers. For example, it may have only one of the layers (1) to (4), or may have two or more.
As the polymer antistatic layer, the layer (1) is preferable because it is easy to produce. Layer (1) and any one or more of layers (2) to (4) may be used in combination.

Adhesive layer 4B2
As the adhesive contained in the adhesive layer 4B2 that is preferably used in the heat-resistant resin layer 4B constituting the laminate of the fourth invention of the present application, a conventionally known adhesive can be appropriately used. From the viewpoint of the manufacturing party of the laminate of the fourth invention of the present application, an adhesive for dry lamination can be preferably used. For example, a polyvinyl acetate adhesive; a homopolymer or copolymer of an acrylic ester (ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), or an acrylic ester and another monomer (methacrylic ester) Polyacrylate adhesives consisting of copolymers with methyl acid, acrylonitrile, styrene, etc .; Cyanoacrylate adhesives; Ethylene and other monomers (vinyl acetate, ethyl acrylate, acrylic acid, methacrylic) An ethylene copolymer adhesive comprising a copolymer with an acid, etc .; a cellulose adhesive; a polyester adhesive; a polyamide adhesive; a polyimide adhesive; an amino resin comprising a urea resin or a melamine resin, etc. Adhesives; phenolic resin adhesives; epoxy adhesives; polyols (polyether polyols) Polyurethane adhesive that crosslinks with isocyanate and / or isocyanurate; reactive (meth) acrylic adhesive; rubber adhesive composed of chloroprene rubber, nitrile rubber, styrene-butadiene rubber, etc .; silicone Adhesives such as inorganic adhesives made of alkali metal silicate, low-melting glass, etc .; other adhesives can be used.

Layer 4B3 containing polymer antistatic agent and adhesive
As the polymer antistatic agent contained in the layer 4B3 containing the polymer antistatic agent and the adhesive suitably used in the heat resistant resin layer 4B constituting the laminate of the fourth invention of the present application, a polymer The same polymer-based antistatic agent as that described above with respect to the layer 4B1 containing the antistatic agent can be suitably used. As the adhesive, the same adhesive as described above with respect to the adhesive layer 4B2 containing the adhesive Can be suitably used.
In the above-mentioned layer (4), when the composition forming the layer (4) is an adhesive, it is a particularly preferable example as an aspect of the layer 4B3 containing a polymer antistatic agent and an adhesive.

Other layers The process release film of the fourth invention of the present application has layers other than the release layer 4A, the heat-resistant resin layer 4B, and the release layer 4A ′ as long as it does not contradict the purpose of the fourth invention of the present application. May be. Details of these other layers are the same as those described for the third invention of the present application.

The total thickness of the process release film of the fourth invention of the present application is not particularly limited, but is preferably 10 to 300 μm, for example, and more preferably 30 to 150 μm. When the total thickness of the release film is in the above range, it is preferable because the handling property when used as a roll is good and the amount of discarded film is small.

Hereinafter, preferred embodiments of the process release film of the fourth invention of the present application will be described more specifically. FIG. 1 is a schematic diagram showing an example of a three-layer process release film. As shown in FIG. 1, the release film 10 has a heat-resistant resin layer 12 and a release layer 16 formed on one surface of the release film 16 with an adhesive layer 14 interposed therebetween.

The release layer 16 is the aforementioned release layer 4A, the heat resistant resin layer 12 is the aforementioned heat resistant resin layer 4B, and the adhesive layer 14 is the aforementioned adhesive layer. The release layer 16 is preferably disposed on the side in contact with the sealing resin in the sealing process; the heat-resistant resin layer 12 is preferably disposed on the side in contact with the inner surface of the mold in the sealing process.

FIG. 2 is a schematic diagram showing an example of a five-layer process release film. Members having the same functions as those in FIG. 1 are denoted by the same reference numerals. As shown in FIG. 2, the release film 20 includes a heat resistant resin layer 12 and a release layer 16 A and a release layer 16 B formed on both surfaces of the release film 16 via an adhesive layer 14. The release layer 16A is the aforementioned release layer 4A, the heat-resistant resin layer 12 is the aforementioned heat-resistant resin layer 4B, the release layer 16B is the aforementioned release layer 4A ', and the adhesive layer 14 is the aforementioned It is an adhesive layer.

The compositions of the release layers 16A and 16B may be the same as or different from each other. The thicknesses of the release layers 16A and 16B may be the same as or different from each other. However, it is preferable that the release layers 16A and 16B have the same composition and thickness as each other because a symmetric structure is obtained and the release film itself is hardly warped. In particular, since the release film of the fourth invention of the present application may be stressed by heating in the sealing process, it is preferable to suppress warpage. As described above, it is preferable that the release layers 16A and 16B are formed on both surfaces of the heat-resistant resin layer 12 because good release properties can be obtained on both the molded product and the inner surface of the mold.

Process Release Film Production Method The process release film of the fourth invention of the present application can be produced by any method, but the preferred production method is the same as that described for the third invention of the present application.

Manufacturing process The release film for a process of the fourth invention of the present application is used by placing a semiconductor chip or the like in a mold and injecting and molding a resin between the semiconductor chip and the inner surface of the mold. Can do. By using the process release film of the fourth invention of the present application, it is possible to effectively prevent mold release failure from the mold, generation of burrs, and the like.
The resin used in the manufacturing process may be either a thermoplastic resin or a thermosetting resin. However, thermosetting resins are widely used in the technical field, and in particular, epoxy-based thermosetting resins are used. It is preferable to use it.
As the above manufacturing process, semiconductor chip sealing is the most representative, but is not limited to this, and the fourth invention of the present application is also applicable to a fiber reinforced plastic molding process, a plastic lens molding process, and the like. Can do.
Details of the manufacturing process using the process release film of the fourth invention of the present application are the same as those described for the third invention of the present application.

The release film of the fourth invention of the present application is not limited to the step of resin-sealing a semiconductor element, but a step of molding and releasing various molded products using a molding die, such as a fiber-reinforced plastic molding and release step, plastic It can also be preferably used in lens molding and mold release processes.

Hereinafter, the first to fourth inventions of the present application will be described in more detail by way of examples. However, the first and second inventions of the present application are not limited in any way.

In the following examples / reference examples, physical properties / characteristics were evaluated by the following methods.
(Thermal dimensional change rate)
The film sample was cut into a length (20 mm) and a width (4 mm) in the longitudinal (MD) direction and transverse (TD) direction of the film, respectively, and the distance between chucks was 8 mm using a TA Instruments TMA (thermomechanical analyzer, product name: Q400). After holding at 23 ° C. for 5 minutes under a load of 0.005 N, the temperature was raised from 23 ° C. to 120 ° C. at a rate of 10 ° C./min, and the dimensional change in each direction was measured. The dimensional change rate was calculated from (1).

Thermal dimensional change rate (%) (23 → 120 ° C.) = {[(L ₂ −L ₁ ) / L ₁ ] × 100}
... (1)
L ₁ : Sample length at 23 ° C. (mm)
L ₂ : Sample length at 120 ° C. (mm)

Similarly, the temperature was raised from 23 ° C. to 170 ° C. at a rate of 10 ° C./min, the dimensional change in each direction was measured, and the dimensional change rate was calculated by the following formula (2).

Thermal dimensional change rate (%) (23 → 170 ° C.) = {[(L ₃ −L ₁ ) / L ₁ ] × 100}
... (2)
L ₁ : Sample length at 23 ° C. (mm)
L ₃ : Sample length at 170 ° C. (mm)

Water contact angle (water contact angle)
Based on JIS R 3 2 5 7, the water contact angle of the surface of the release layer A or the like was measured using a contact angle measuring device (manufactured by Kyowa Interface Science, FACECA-W).

(Tensile modulus)
Measurement method of tensile elastic modulus Based on JIS K7127, the tensile elastic modulus at 23 ° C, 120 ° C and 170 ° C was determined.
Measurement conditions: Tensile mode Measurement direction: Film longitudinal (MD) direction (film transport direction)

(Surface specific resistance)
A 10 × 10 cm test piece cut out from the obtained release film was stored at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours. Thereafter, the applied voltage was measured at 0.10 V, a temperature of 23 ° C., and a humidity of 50% RH using a digital ultra-high resistance / trace ammeter (8340A) manufactured by Advantest Corporation and a resistance chamber (R12704).

(Ashes adhesion test)
The antistatic property of the release film was determined by examining the adhesion of ash after rubbing the release film 10 times with a polyester fiber cloth in an atmosphere of 20 ° C. and 50% RH.
No adhesion: ○
Adhesion is remarkable: ×
It was.

(Melting point (Tm), heat of crystal melting)
Using a Q100 manufactured by TA Instruments Inc. as a differential scanning calorimeter (DSC), about 5 mg of a polymer sample is precisely weighed, and in accordance with JISK7121, a nitrogen gas inflow rate of 50 ml / min is 25. The heat melting curve was measured by heating from ℃ to 280 ° C. at a heating rate of 10 ° C./min, and the melting point (Tm) and the crystal melting heat amount of the sample were determined from the obtained heat melting curve.

(Releasability)
After the process release film produced in each Example / Reference Example is placed with 10N tension applied between the upper mold and the lower mold as shown in FIGS. The vacuum was adsorbed on the upper parting surface. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 120 ° C., the molding pressure was 10 MPa, and the molding time was 400 seconds. Then, as shown in FIGS. 3-1c and 3-2c, after the semiconductor chip was sealed with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film.
The releasability of the release film was evaluated according to the following criteria.
A: The release film naturally peels off at the same time as the mold is opened.
○: The release film does not peel off naturally, but peels easily when pulled by hand (applying tension).
X: The release film is in close contact with the resin sealing surface of the semiconductor package and cannot be peeled off by hand.

(wrinkle)
The state of wrinkles on the release film and the resin sealing surface of the semiconductor package after release in the above process was evaluated according to the following criteria.
A: There is no wrinkle at all in the release film and the semiconductor package.
○: The release film has slight wrinkles, but there is no transfer of wrinkles to the semiconductor package.
X: There are many defects in the semiconductor package as well as the release film.

(Appearance of molded product)
The appearance of the release film and the resin sealing surface of the semiconductor package after release in the above process was evaluated according to the following criteria.
A: There are no wrinkles in the release film and the semiconductor package, and there is no burr on the outer periphery of the semiconductor package.
○: There are no wrinkles or slight wrinkles in both the release film and the semiconductor package, and there are slight burrs on the outer periphery of the semiconductor package.
X: There are many wrinkles in the semiconductor package as well as the release film, or there are many burrs on the outer periphery of the semiconductor package.

(Mold followability)
The mold following property of the release film at the time of releasing in the above process was evaluated according to the following criteria.
A: The semiconductor package does not have any resin deficiency (portion not filled with resin).
○: There is a slight resin chip at the edge of the semiconductor package (excluding chipping due to defects) ×: There are many resin defects at the edge of the semiconductor package (excluding chipping due to defects)

[Example 1-1]
A biaxially stretched PET (polyethylene terephthalate) film (product name: Lumirror F865 manufactured by Toray Industries, Inc.) having a film thickness of 16 μm was used as the heat resistant resin layer 1B. The thermal dimensional change rate from 23 ° C. to 120 ° C. of the biaxially stretched PET film was −1.6% in the machine (MD) direction and −1.2% in the transverse (TD) direction. Moreover, the melting point of the biaxially stretched PET film was 187 ° C., and the heat of crystal fusion was 30.6 J / g.

As the release layers 1A and 1A ′, unstretched 4-methyl-1-pentene copolymer resin films were used. Specifically, 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. is melt extruded at 270 ° C. to adjust the slit width of the T-type die. Thus, a non-stretched film having a thickness of 15 μm was used.
The non-stretched 4-methyl-1-pentene copolymer resin film has improved adhesion by an adhesive so that one film surface has a water contact angle of 30 ° or more based on JIS R3257, which is 30 or less. Corona treatment was applied from the viewpoint.
The thermal dimensional change rate from 23 ° C. to 120 ° C. of the 4-methyl-1-pentene copolymer resin film was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction. .

(adhesive)
The following urethane-based adhesive A was used as the adhesive used in the dry lamination process for bonding each film.
[Urethane adhesive A]
Main agent: Takelac A-616 (manufactured by Mitsui Chemicals). Curing agent: Takenate A-65 (Mitsui Chemicals). The main agent and the curing agent were mixed so that the mass ratio (main agent: curing agent) was 16: 1, and ethyl acetate was used as a diluent.

(Manufacture of release film)
One side of a biaxially stretched PET (polyethylene terephthalate) film was coated with 1.5 g / m ² of urethane adhesive A by gravure coating, and an unstretched 4-methyl-1-pentene copolymer resin film After laminating the corona-treated surfaces by dry lamination, urethane adhesive A was applied at 1.5 g / m ² on the side of the biaxially stretched PET (polyethylene terephthalate) film surface of the laminate film. The corona-treated surface of the stretched 4-methyl-1-pentene copolymer resin film is bonded by dry lamination to form a 5-layer structure (release layer 1A / adhesive layer / heat-resistant resin layer 1B / adhesive layer / release layer 1A). ') A release film for the process was obtained.
The dry lamination conditions were a substrate width of 900 mm, a conveyance speed of 30 m / min, a drying temperature of 50 to 60 ° C., a laminate roll temperature of 50 ° C., and a roll pressure of 3.0 MPa.

The thermal dimensional change rate from 23 ° C. to 120 ° C. of the release film for the process was 2.1% in the machine direction (MD) and 1.5% in the transverse (TD) direction.
Table 1-1 shows the evaluation results of releasability, wrinkles, and mold followability. The release film exhibits good release properties that peel off spontaneously at the same time as the mold is opened, and there is no wrinkle in both the release film and the semiconductor package, that is, wrinkles are sufficiently suppressed, and the semiconductor package lacks resin. The mold following ability was excellent without any. That is, the process release film of Example 1-1 was a process release film having good release properties, suppression of wrinkles, and mold followability.

[Examples 1-2 to 1-12]
A process release film was prepared in the same manner as in Example 1-1 except that the films shown in Table 1-1 were used as the release layers 1A and 1A ′ and the heat-resistant resin layer 1B in the combinations shown in Table 1-1. It produced, sealed and released, and evaluated the characteristic. The results are shown in Table 1-1.
In some cases, the suppression of wrinkles or mold followability did not reach that of Example 1-1. However, all the examples had high levels of mold release, wrinkle suppression, and mold followability. It was a well-balanced release film for process use

The details of each film listed in Table 1-1 are as follows.
(1A1) Non-stretched 4MP-1 (TPX) film A 15 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(1A2) Unstretched 4MP-1 (TPX) film A 15 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: DX818) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 235 ° C., heat of crystal melting: 28.1 J / g)
(1A3) Unstretched 4MP-1 (TPX) film A 50 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(1A4) Unstretched 4MP-1 (TPX) film A non-stretched film having a thickness of 50 μm was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: DX818) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 235 ° C., heat of crystal melting: 28.1 J / g)
(1A5) Fluororesin film 25 μm thick ETFE (ethylene-tetrafluoroethylene) film (Asahi Glass Co., Ltd., product name: Aflex 25N) (melting point: 256 ° C., heat of crystal melting: 33.7 J / g)
(1A6) Polystyrene resin film Polystyrene film with a film thickness of 50 μm (manufactured by Kurashiki Boseki Co., Ltd., product name: Eudis CA-F) (melting point: 253 ° C., heat of crystal melting: 19.2 J / g)
(1B1) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 16 μm (manufactured by Toray Industries, Inc., product name: Lumirror F865) (melting point: 187 ° C., heat of crystal melting: 30.6 J / g)
(1B2) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 12 μm (product name: Lumirror S10, manufactured by Toray Industries, Inc.) (melting point: 258 ° C., heat of crystal melting: 39.4 J / g)
(1B3) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (manufactured by Kojin Film & Chemicals Co., Ltd., product name: Bonyl RX) (melting point: 212 ° C., heat of crystal melting: 53.1 J / g)
(1B4) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (product name: UNILON S330, manufactured by Idemitsu Unitech Co., Ltd.) (melting point: 221 ° C., heat of crystal melting: 60.3 J / g)
(1B5) Biaxially stretched polypropylene film Biaxially stretched polypropylene film with a film thickness of 20 μm (Mitsui Chemicals Tosero Co., Ltd., product name: U-2) (melting point: 160 ° C., heat of crystal melting: 93.3 J / g)
(1B6) Unstretched nylon film Unstretched nylon film with a film thickness of 20 μm (Mitsubishi Resin Co., Ltd., product name: Dynamilon C) (melting point: 220 ° C., heat of crystal melting: 39.4 J / g)
(1B7) Biaxially stretched PET film Biaxially stretched PET film with a film thickness of 25 μm (manufactured by Teijin DuPont Films, product name: FT3PE) (melting point: 214 ° C., heat of crystal melting: 40.3 J / g)
(1B8) Non-stretched polybutylene terephthalate film A film obtained by forming a 20 μm-thick unstretched film using polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(1B9) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm is formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)
(1B10) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm is formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(1B11) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)

[Reference Examples 1-1 to 1-4]
Films 1A3, 1A4, 1B10, and 1B11 shown in Table 1-1 were each used as a process release film, and sealed and released in the same manner as in Example 1-1 to obtain a process release. The properties of the mold film were evaluated.
In any of the reference examples, the performance was not as good as the comprehensive example, and the generation of wrinkles could not be particularly suppressed.

[Examples 13 to 20]
In the same manner as in Example 1-1, release films for processes were used in the same manner as in Example 1-1, using release films in which the films shown in Table 1-2 were used as release layers 1A and 1A ′ and heat-resistant resin layer 1B in the combinations shown in Table 1-2. A mold film was prepared, sealed and released, and evaluated for characteristics.
As shown in FIG. 4, the release film was placed in a state where a tension of 20 N was applied between the upper mold and the lower mold, and then vacuum-adsorbed on the upper parting surface. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 170 ° C., the molding pressure was 10 MPa, and the molding time was 100 seconds. Then, as shown in FIG. 3C, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film. The results are shown in Table 1-2.
Although some of the mold followability did not reach that of Example 1-1, each of the examples had a good process with a balance between mold release, wrinkle suppression, and mold followability. In particular, Example 1-11 and Examples 1-13 to 1-15 were process release films having good release properties, suppression of wrinkles, and mold followability. .

[Reference Examples 1-5 to 1-7]
A process similar to that in Examples 1-11 to 1-16 except that the films shown in Table 1-2 were used as the release layers 1A and 1A ′ and the heat-resistant resin layer 1B in the combinations shown in Table 1-2. A mold release film was prepared, sealed and released, and evaluated for characteristics. The results are shown in Table 1-2.
Although mold release property and mold followability were good as in the examples, the generation of wrinkles could not be suppressed.

[Reference Examples 1-8 to 1-11]
Films 1A1, 1A2, 1B10, and 1B11 shown in Table 1-2 were each used as a process release film, and sealed and released in the same manner as in Examples 1-11 to 1-16. The characteristics of the release film for process were evaluated.
All of the reference examples generally had performances that did not reach the respective examples, and in particular, generation of wrinkles could not be suppressed.

[Example 2-1]
A biaxially stretched PET (polyethylene terephthalate) film (product name: Lumirror F865, manufactured by Toray Industries, Inc.) having a film thickness of 16 μm was used as the base material 2B0a of the heat-resistant resin layer 2B.
As the antistatic resin a, a PEDOT polythiophene resin (product name: MC-200, manufactured by Kaken Sangyo Co., Ltd.) was used to form a layer containing a polymer antistatic agent. More specifically, the antistatic resin a is applied to one side of the base material 2B0a of the heat-resistant resin layer 2B at a coating amount of 0.1 g / m ² and dried to obtain a layer 2B1a containing a polymer antistatic agent. Formed.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. of the biaxially stretched PET film (heat-resistant resin layer 2Ba) provided with the layer containing the polymer antistatic agent obtained above is in the longitudinal (MD) direction. 1.8% and -1.4% in the transverse (TD) direction. Moreover, the melting point of the biaxially stretched PET film was 187 ° C., and the heat of crystal fusion was 30.6 J / g.

As the release layers 2A and 2A ′, unstretched 4-methyl-1-pentene copolymer resin film 2Aa (2A′a) was used. Specifically, 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. is melt extruded at 270 ° C. to adjust the slit width of the T-type die. Thus, a non-stretched film having a thickness of 15 μm was used.
The non-stretched 4-methyl-1-pentene copolymer resin film has improved adhesion by an adhesive so that one film surface has a water contact angle of 30 ° or more based on JIS R3257, which is 30 or less. Corona treatment was applied from the viewpoint.
The thermal dimensional change rate from 23 ° C. to 120 ° C. of the 4-methyl-1-pentene copolymer resin film Aa was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction. It was.

(adhesive)
The following urethane adhesive α was used as an adhesive used in the dry lamination process for bonding the films.
[Urethane adhesive α]
Main agent: Takelac A-616 (manufactured by Mitsui Chemicals). Curing agent: Takenate A-65 (Mitsui Chemicals). The main agent and the curing agent were mixed so that the mass ratio (main agent: curing agent) was 16: 1, and ethyl acetate was used as a diluent.

(Manufacture of release film)
One surface of the biaxially stretched PET film (heat resistant resin layer 2Ba) provided with the antistatic layer was coated with 1.5 g / m ² of urethane adhesive α by gravure coating, and unstretched 4-methyl After the corona-treated surfaces of the -1-pentene copolymer resin film 2Aa are bonded together by dry lamination, 1.5 g / m ^{2 of} urethane adhesive α is subsequently applied to the biaxially stretched PET film surface side of the laminate film. The corona-treated surface of unstretched 4-methyl-1-pentene copolymer resin film 2A'a is bonded by dry lamination to form a five-layer structure (release layer 2A / adhesive layer / heat-resistant resin layer) A release film for process of 2B / adhesive layer / release layer 2A ′) was obtained.
The dry lamination conditions were a substrate width of 900 mm, a conveyance speed of 30 m / min, a drying temperature of 50 to 60 ° C., a laminate roll temperature of 50 ° C., and a roll pressure of 3.0 MPa.

The thermal dimensional change rate of the process release film from 23 ° C. to 120 ° C. was 2.2% in the machine direction (MD) and 1.4% in the transverse (TD) direction.
Table 2-1 shows the evaluation results of releasability, appearance of the molded product, and mold followability. The mold release film shows good mold release properties that peel off spontaneously at the same time as the mold is opened, and neither the mold release film nor the semiconductor package has any wrinkles or burrs. Good mold followability with no resin chipping. That is, the process release film of Example 2-1 was a process release film having good release properties, appearance of the molded product, and mold followability.

[Examples 2-2 to 2-8]
A process release film was prepared in the same manner as in Example 2-1, except that the film configuration shown in Table 2-1 was used, and sealing and release were performed to evaluate the characteristics. The results are shown in Table 2-1.
The details of the polymer antistatic agents 2b to 2e and the layers 2B1b to 2B1e containing the same as described in Table 2-1 are as follows.
As the antistatic resin 2b, a PEDOT polythiophene resin (manufactured by Chukyo Yushi Co., Ltd., product name: S-495) was used to form a layer containing a polymer antistatic agent. More specifically, the antistatic resin 2b is applied to one side of the heat-resistant resin layer 2B, such as the base material 2B0a, at a coating amount of 0.3 g / m ² and dried to contain a polymer antistatic agent. 2B1b was formed. The rate of thermal dimensional change from 23 ° C. to 120 ° C. of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above was the result shown in Table 2-1.
As the antistatic resin 2c, a PEDOT polythiophene resin (manufactured by Nagase Sangyo Co., Ltd., product name: P-530RL) was used to form a layer containing a polymer antistatic agent. More specifically, the antistatic resin 2c is coated on one surface of the heat-resistant resin layer 2B such as the base material 2B0a at a coating amount of 0.1 g / m ² and dried to contain a polymer antistatic agent. 2B1c was formed. The rate of thermal dimensional change from 23 ° C. to 120 ° C. of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above was the result shown in Table 2-1.
As the antistatic resin 2d, a quaternary ammonium salt-containing resin (manufactured by Taisei Fine Chemical Co., Ltd., product name: 1SX-1090) was used to form a layer containing a polymeric antistatic agent. More specifically, the antistatic resin 2d is applied to one surface of the heat-resistant resin layer 2B, such as the base material 2B0a, at a coating amount of 0.4 g / m ² and dried to contain a polymer antistatic agent. 2B1d was formed. The rate of thermal dimensional change from 23 ° C. to 120 ° C. of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above was the result shown in Table 2-1.
As the antistatic resin 2e, an anionic synthetic clay mineral-containing polyester resin (manufactured by Takamatsu Yushi Co., Ltd., product name: ASA-2050) was used to form a layer containing a polymer antistatic agent. Specifically, the antistatic resin 2e is applied to one side of the heat-resistant resin layer 2B, such as the base material 2B0a, at a coating amount of 0.4 g / m ² and dried to contain the polymer antistatic agent 2B1e. Formed. The test items and evaluation results, such as thermal dimensional change rate from 23 ° C. to 120 ° C. and water contact angle, of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above are shown in Table 2- As shown in FIG.

All of the examples were process release films that were good in all test items of releasability, appearance of molded products, mold followability, and ash adhesion test, and balanced in terms of performance.

In addition, the detail of each film as described in a table | surface is as follows.
(2Aa) Unstretched 4MP-1 (TPX) film A 15 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(2Ab) Unstretched 4MP-1 (TPX) film A 50 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(2Ac) Fluororesin film 25 μm thick ETFE (ethylene-tetrafluoroethylene) film (Asahi Glass Co., Ltd., product name: Aflex 25N) (melting point: 256 ° C., heat of crystal melting: 33.7 J / g)
(2B0a) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 16 μm (product name: Lumirror F865, manufactured by Toray Industries, Inc.) (melting point: 187 ° C., heat of crystal melting: 30.6 J / g)
(2B0b) Biaxially stretched polypropylene film Biaxially stretched polypropylene film with a film thickness of 20 μm (Mitsui Chemicals Tosero Co., Ltd., product name: U-2) (melting point: 160 ° C., heat of crystal melting: 93.3 J / g)
(2B0c) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm is formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)
(2B0d) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (product name: UNILON S330, manufactured by Idemitsu Unitech Co., Ltd.) (melting point: 221 ° C., heat of crystal melting: 60.3 J / g)
(2B0e) Unstretched nylon film Unstretched nylon film having a film thickness of 20 μm (product name: Dynamilon C, manufactured by Mitsubishi Plastics, Inc.) (melting point: 220 ° C., heat of crystal melting: 39.4 J / g)
(2B0f) Biaxially stretched PET film Biaxially stretched PET film with a thickness of 25 μm (manufactured by Teijin DuPont Films, product name: FT3PE) (melting point: 214 ° C., heat of crystal melting: 40.3 J / g)
(2B0g) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics Co., Ltd. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(2B0h) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)

[Reference Examples 2-1 to 2-4]
Except for the film configuration shown in Table 2-1, sealing and mold release were performed in the same manner as in Example 2-1, and the characteristics of the process release film were evaluated.
In all the reference examples, the performance was not as good as the overall example, and the appearance of the molded product was particularly inferior. Further, in the ash adhesion test, good results were not obtained except for Reference Example 2-2.

[Examples 2-9 to 2-16]
A process release film was prepared in the same manner as in Example 2-1, except that each film shown in Table 2-2 was changed to the release layers 2A and 2A ′ and the heat-resistant resin layer 2B in the combinations shown in Table 2-2. Then, sealing and releasing were performed, and the characteristics were evaluated.
As shown in FIG. 3a, the release film was placed between the upper mold and the lower mold in a state where a tension of 20N was applied, and then was vacuum-adsorbed on the parting surface of the upper mold. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 170 ° C., the molding pressure was 10 MPa, and the molding time was 100 seconds. Then, as shown in FIG. 3c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film. The results are shown in Table 2-2.
In all the examples, despite the evaluation of the high temperature range at 170 ° C., the mold release property, the appearance of the molded product, and the mold followability are good in all the test items of the ash adhesion test, and are balanced from the viewpoint of performance. It was a release film for process. In particular, Example 2-11 and Examples 2-13 to 2-15 were process release films having good release properties, appearance of molded products, and mold followability.

[Reference Examples 2-5 to 2-7]
A process release film was prepared in the same manner as in Examples 2-11 to 2-16 except that the film configuration shown in Table 2-2 was used, and the film was sealed and released, and the characteristics were evaluated. . The results are shown in Table 2-2.
The releasability was good as in the examples, but the generation of wrinkles could not be suppressed, and the appearance of the molded product was inferior. Further, in the ash adhesion test, good results were not obtained except Reference Example 2-6.

[Reference Examples 2-8 to 2-10]
Except for the film configuration shown in Table 2-2, sealing and mold release were performed in the same manner as in Example 2-9, and the characteristics of the process release film were evaluated. The results are shown in Table 2-2.
All of the reference examples generally had performances that did not reach each of the examples. In particular, the occurrence of wrinkles could not be suppressed, and the appearance of the molded product was inferior.

Hereinafter, the third and fourth inventions of the present application will be described in more detail by way of examples. However, the third and fourth inventions of the present application are not limited in any way by this example.

Water contact angle (water contact angle)
Based on JIS R3257, the water contact angle on the surface of the release layer A or the like was measured using a contact angle measuring device (manufactured by Kyowa Interface Science, FACECA-W).
(Tensile modulus)
Measurement method of tensile elastic modulus Based on JIS K7127, the tensile elastic modulus at 23 ° C, 120 ° C and 170 ° C was determined.
Measurement conditions: Tensile mode Measurement direction: Film longitudinal (MD) direction (film transport direction)

(Ash adhesion test)
The antistatic property of the release film was determined by examining the adhesion of ash after rubbing the release film 10 times with a polyester fiber cloth in an atmosphere of 20 ° C. and 50% RH.
No adhesion: ○
Adhesion is remarkable: ×
It was.

(Releasability)
As shown in FIG. 3, the process release film produced in each example / reference example was placed in a state where a tension of 10 N was applied between the upper mold and the lower mold, and then the upper mold parting was performed. The surface was vacuum-adsorbed. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 120 ° C., the molding pressure was 10 MPa, and the molding time was 400 seconds. Then, as shown in FIG. 3c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film.
The releasability of the release film was evaluated according to the following criteria.
A: The release film naturally peels off at the same time as the mold is opened.
○: The release film does not peel off naturally, but peels easily when pulled by hand (applying tension).
X: The release film is in close contact with the resin sealing surface of the semiconductor package and cannot be peeled off by hand.

[Example 3-1]
A biaxially stretched PET (polyethylene terephthalate) film (product name: Lumirror S10 manufactured by Toray Industries, Inc.) having a film thickness of 12 μm was used as the heat resistant resin layer 3B. The thermal dimensional change rate from 23 ° C. to 120 ° C. of the biaxially stretched PET film was −0.3% in the machine direction (MD) and −0.3% in the transverse (TD) direction. Moreover, the melting point of the biaxially stretched PET film was 258 ° C., and the heat of crystal fusion was 39.4 J / g.

As the release layers 3A and 3A ′, unstretched 4-methyl-1-pentene copolymer resin films were used. Specifically, 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. is melt extruded at 270 ° C. to adjust the slit width of the T-type die. Thus, a non-stretched film having a thickness of 15 μm was used.
The non-stretched 4-methyl-1-pentene copolymer resin film has improved adhesion by an adhesive so that one film surface has a water contact angle of 30 ° or more based on JIS R3257, which is 30 or less. Corona treatment was applied from the viewpoint.
The thermal dimensional change rate from 23 ° C. to 120 ° C. of the 4-methyl-1-pentene copolymer resin film was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction. .

(Manufacture of release film)
One side of a biaxially stretched PET (polyethylene terephthalate) film was coated with 1.5 g / m ² of urethane adhesive A by gravure coating, and an unstretched 4-methyl-1-pentene copolymer resin film After laminating the corona-treated surfaces by dry lamination, urethane adhesive A was applied at 1.5 g / m ² on the side of the biaxially stretched PET (polyethylene terephthalate) film surface of the laminate film. The corona-treated surface of the stretched 4-methyl-1-pentene copolymer resin film is bonded by dry lamination to form a 5-layer structure (release layer 3A / adhesive layer / heat-resistant resin layer 3B / adhesive layer / release layer 3A). ') A release film for the process was obtained.
The dry lamination conditions were a substrate width of 900 mm, a conveyance speed of 30 m / min, a drying temperature of 50 to 60 ° C., a laminate roll temperature of 50 ° C., and a roll pressure of 3.0 MPa.

The thermal dimensional change rate from 23 ° C. to 120 ° C. of the release film for the process was 2.1% in the machine direction (MD) and 1.5% in the transverse (TD) direction.
Table 3-1 shows the evaluation results of releasability, wrinkles, and mold followability. The release film exhibits good release properties that peel off spontaneously at the same time as the mold is opened, and there is no wrinkle in both the release film and the semiconductor package, that is, wrinkles are sufficiently suppressed, and the semiconductor package lacks resin. The mold following ability was excellent without any. That is, the process release film of Example 3-1 was a process release film having good release characteristics, suppression of wrinkles, and mold followability.

[Examples 3-2 to 3-9]
A process release film was prepared in the same manner as in Example 3-1, except that the films shown in Table 3-1 were used as the release layers 3A and 3A ′ and the heat-resistant resin layer 3B in the combinations shown in Table 3-1. It produced, sealed and released, and evaluated the characteristic. The results are shown in Table 3-1.
In some cases, wrinkle suppression or mold followability did not reach that of Example 3-1, but all of the examples had high levels of mold release, wrinkle suppression, and mold followability. It was a well-balanced release film for process use

In addition, the detail of each film as described in a table | surface is as follows.
(3A1) Unstretched 4MP-1 (TPX) film A 15 μm-thick unstretched film was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(3A2) Unstretched 4MP-1 (TPX) film A non-stretched film with a thickness of 15 μm was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: DX818) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 235 ° C., heat of crystal melting: 28.1 J / g)
(3A3) Unstretched 4MP-1 (TPX) film A non-stretched film having a thickness of 50 μm was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(3B1) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 12 μm (manufactured by Toray Industries, Inc., product name: Lumirror S10) (melting point: 258 ° C., heat of crystal melting: 39.4 J / g)
(3B2) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (manufactured by Kojin Film & Chemicals Co., Ltd., product name: Bonyl RX) (melting point: 212 ° C., heat of crystal melting: 53.1 J / g)
(3B3) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (product name: UNILON S330, manufactured by Idemitsu Unitech Co., Ltd.) (melting point: 221 ° C., heat of crystal melting: 60.3 J / g)
(3B4) Biaxially stretched polypropylene film Biaxially stretched polypropylene film with a film thickness of 20 μm (Mitsui Chemicals Tosero Co., Ltd., product name: U-2) (melting point: 160 ° C., heat of crystal melting: 93.3 J / g)
(3B5) Unstretched nylon film Unstretched nylon film with a film thickness of 20 μm (product name: Dynamilon C, manufactured by Mitsubishi Plastics, Inc.) (melting point: 220 ° C., heat of crystal melting: 39.4 J / g)
(3B6) Biaxially stretched PET film Biaxially stretched PET film with a film thickness of 25 μm (manufactured by Teijin DuPont Films, product name: FT3PE) (melting point: 214 ° C., heat of crystal melting: 40.3 J / g)
(3B7) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics Co., Ltd. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(3B8) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics Co., Ltd. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)
(3B9) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm formed using a polybutylene terephthalate resin (brand name: 5020) manufactured by Mitsubishi Engineering Plastics. (Melting point: 223 ° C., heat of crystal melting: 49.8 J / g)
(3B10) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm is formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)

[Reference Examples 3-1 to 3-3]
Using the films 3A3, 3B9, and 3B10 shown in Table 3-1 alone as a process release film, sealing and releasing were performed in the same manner as in Example 3-1, and the process release film was used. The characteristics were evaluated.
In any of the reference examples, the performance was not as good as the comprehensive example, and the generation of wrinkles could not be particularly suppressed.

[Examples 3-10 to 3-14]
In the same manner as in Example 3-1, release films for processes were used in the same manner as in Example 3-1, using release films in which the films shown in Table 3-2 were used as release layers 3A and 3A ′ and heat-resistant resin layer 3B in the combinations shown in Table 3-2. A mold film was prepared, sealed and released, and evaluated for characteristics.
As shown in FIG. 4, the release film was placed in a state where a tension of 20 N was applied between the upper mold and the lower mold, and then vacuum-adsorbed on the upper parting surface. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 170 ° C., the molding pressure was 10 MPa, and the molding time was 100 seconds. Then, as shown in FIG. 3c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film. The results are shown in Table 3-2.
Although some of the mold followability did not reach that of Example 3-1, each example had a good process that balanced the mold release property, the suppression of wrinkles, and the mold followability at a high level. In particular, Examples 3-11 to 3-13 were process release films having good release properties, suppression of wrinkles, and mold followability.

[Reference Examples 3-4 to 3-6]
A process similar to that in Examples 3-10 to 3-14 except that the films shown in Table 3-2 were used as the release layers 3A and 3A ′ and the heat-resistant resin layer 3B in the combinations shown in Table 3-2. A mold release film was prepared, sealed and released, and evaluated for characteristics. The results are shown in Table 3-2.
Although mold release property and mold followability were good as in the examples, the generation of wrinkles could not be suppressed.

[Reference Examples 3-7 to 3-10]
Films 3A1, 3A2, 3B9, and 3B10 shown in Table 3-2 were each used alone as a process release film, and sealed and released in the same manner as in Examples 3-10 to 3-14. The characteristics of the release film for process were evaluated.
All of the reference examples generally had performances that did not reach the respective examples, and in particular, generation of wrinkles could not be suppressed.

[Example 4-1]
As the base material 4B0a of the heat-resistant resin layer 4B, a biaxially stretched PET (polyethylene terephthalate) film (manufactured by Toray Industries, Inc., product name: Lumirror S10) having a film thickness of 12 μm was used.
As the antistatic resin 4a, a PEDOT polythiophene resin (product name: MC-200, manufactured by Kaken Sangyo Co., Ltd.) was used to form a layer containing a polymer antistatic agent. More specifically, the antistatic resin 4a is applied to one surface of the base material 4B0a of the heat-resistant resin layer 4B at a coating amount of 0.1 g / m ² and dried to contain the polymer antistatic agent 4B1a. Formed.
The rate of thermal dimensional change from 23 ° C. to 120 ° C. of the biaxially stretched PET film (heat-resistant resin layer 4Ba) provided with the layer containing the polymer antistatic agent obtained above is in the longitudinal (MD) direction − 0.1% and 0.6% in the transverse (TD) direction. Moreover, the melting point of the biaxially stretched PET film was 258 ° C., and the heat of crystal fusion was 39.4 J / g.

As the release layers 4A and 4A ′, unstretched 4-methyl-1-pentene copolymer resin film 4Aa (4A′a) was used. Specifically, an unstretched film having a thickness of 15 μm was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
The non-stretched 4-methyl-1-pentene copolymer resin film has improved adhesion by an adhesive so that one film surface has a water contact angle of 30 ° or more based on JIS R3257, which is 30 or less. Corona treatment was applied from the viewpoint.
The thermal dimensional change rate from 23 ° C. to 120 ° C. of the 4-methyl-1-pentene copolymer resin film 4Aa was 6.5% in the longitudinal (MD) direction and 3.1% in the transverse (TD) direction. It was.

(Manufacture of release film)
On one surface of the biaxially stretched PET film (heat-resistant resin layer 4Ba) provided with the antistatic layer, urethane adhesive α was applied at 1.5 g / m ² by gravure coating, and unstretched 4-methyl After the corona-treated surfaces of the -1-pentene copolymer resin film 4Aa are bonded together by dry lamination, 1.5 g / m ^{2 of} urethane-based adhesive α is subsequently applied to the biaxially stretched PET film surface side of the laminate film. The corona-treated surface of the unstretched 4-methyl-1-pentene copolymer resin film 4A'a is bonded by dry lamination to form a five-layer structure (release layer 4A / adhesive layer / heat-resistant resin layer) A release film for process of 4B / adhesive layer / release layer 4A ′) was obtained.
The dry lamination conditions were a substrate width of 900 mm, a conveyance speed of 30 m / min, a drying temperature of 50 to 60 ° C., a laminate roll temperature of 50 ° C., and a roll pressure of 3.0 MPa.

The thermal dimensional change rate from 23 ° C. to 120 ° C. of the release film for the process was 1.0% in the longitudinal (MD) direction and 1.4% in the transverse (TD) direction.
Table 4-1 shows the evaluation results of tensile modulus, releasability, appearance of molded product, mold followability, surface resistivity, and ash adhesion test. The mold release film shows good mold release properties that peel off spontaneously at the same time as the mold is opened, and neither the mold release film nor the semiconductor package has any wrinkles or burrs. Good mold followability with no resin chipping. That is, the process release film of Example 4-1 was a process release film having good release properties, appearance of the molded product, and mold followability. Moreover, no ash adhesion was observed.

[Examples 4-2 to 4-9]
A process release film was prepared in the same manner as in Example 4-1, except that the film configuration shown in Table 4-1 was used, and sealing and release were performed to evaluate the characteristics. The results are shown in Table 4-1.
The details of the polymer antistatic agents 4b to 4e and the layers 4B1b to 4B1e containing the polymer antistatic agents described in Table 4-1 are as follows.
As the antistatic resin 4b, a PEDOT polythiophene resin (manufactured by Chukyo Yushi Co., Ltd., product name: S-495) was used to form a layer containing a polymer antistatic agent. More specifically, the antistatic resin 4b is coated on one surface of the heat-resistant resin layer 4B such as the base material 4B0a at a coating amount of 0.3 g / m ² and dried to contain a polymer antistatic agent. 4B1b was formed. The thermal dimensional change rate from 23 ° C. to 120 ° C. of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above was the result shown in Table 4-1.
As the antistatic resin 4c, a PEDOT polythiophene resin (manufactured by Nagase Sangyo Co., Ltd., product name: P-530RL) was used to form a layer containing a polymer antistatic agent. More specifically, the antistatic resin 4c is applied to one side of the heat-resistant resin layer 4B, such as the base material 4B0a, at a coating amount of 0.1 g / m ² and dried to contain a polymer antistatic agent. 4B1c was formed. The thermal dimensional change rate from 23 ° C. to 120 ° C. of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above was the result shown in Table 4-1.
As the antistatic resin 4d, a quaternary ammonium salt-containing resin (manufactured by Taisei Fine Chemical Co., Ltd., product name: 1SX-1090) was used to form a layer containing a polymeric antistatic agent. More specifically, the antistatic resin 4d is applied to one surface of the heat-resistant resin layer 4B, such as the base material 4B0a, at a coating amount of 0.4 g / m ² and dried to contain a polymer antistatic agent. 4B1d was formed. The thermal dimensional change rate from 23 ° C. to 120 ° C. of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above was the result shown in Table 4-1.
As the antistatic resin 4e, a polyester resin containing an anionic synthetic clay mineral (manufactured by Takamatsu Yushi Co., Ltd., product name: ASA-2050) was used to form a layer containing a polymer antistatic agent. Specifically, the antistatic resin 4e is applied to one side of the heat-resistant resin layer 4B, such as the base material 4B0a, at a coating amount of 0.4 g / m ² and dried to contain the polymer antistatic agent 4B1e. Formed.

An anionic synthetic clay mineral-containing polyester resin (product name: ASA-2050, manufactured by Takamatsu Yushi Co., Ltd.) was used to form a layer containing a polymeric antistatic agent. Specifically, the antistatic resin 4e is applied to one side of the heat-resistant resin layer 4B, such as the base material 4B0a, at a coating amount of 0.4 g / m ² and dried to contain the polymer antistatic agent 4B1e. Formed. Table 4- shows the test items and evaluation results of the biaxially stretched PET film provided with the layer containing the polymer antistatic agent obtained above, such as the thermal dimensional change rate from 23 ° C. to 120 ° C. and the water contact angle. As shown in FIG.

The details of each film listed in Table 4-1 are as follows.
(4Aa) Unstretched 4MP-1 (TPX) film Using a 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, an unstretched film having a thickness of 15 μm is formed. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(4Ab) Unstretched 4MP-1 (TPX) film A non-stretched film having a thickness of 50 μm was formed using 4-methyl-1-pentene copolymer resin (product name: TPX, brand name: MX022) manufactured by Mitsui Chemicals, Inc. What you did. (Melting point: 229 ° C., heat of crystal melting: 21.7 J / g)
(4B0a) Biaxially stretched PET film Biaxially stretched PET (polyethylene terephthalate) film with a film thickness of 12 μm (product name: Lumirror S10, manufactured by Toray Industries, Inc.) (melting point: 258 ° C., heat of crystal melting: 39.4 J / g)
(4B0b) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (manufactured by Kojin Film & Chemicals Co., Ltd., product name: Bonil RX) (melting point: 212 ° C., heat of crystal melting: 53.1 J / g)
(B0c) Biaxially stretched polypropylene film Biaxially stretched polypropylene film with a film thickness of 20 μm (Mitsui Chemicals Tosero Co., Ltd., product name: U-2) (melting point: 160 ° C., heat of crystal melting: 93.3 J / g)
(4B0d) Unstretched nylon film Unstretched nylon film with a film thickness of 20 μm (product name: Dynamilon C, manufactured by Mitsubishi Plastics, Inc.) (melting point: 220 ° C., heat of crystal melting: 39.4 J / g)
(4B0e) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 20 μm formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics Co., Ltd. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)
(4B0f) Unstretched polybutylene terephthalate film An unstretched film having a thickness of 50 μm formed using a polybutylene terephthalate resin (brand name: 5505S) manufactured by Mitsubishi Engineering Plastics. (Melting point: 219 ° C., crystal melting heat: 48.3 J / g)

[Reference Examples 4-1 to 4-3]
Except for the film configuration shown in Table 4-1, sealing and mold release were performed in the same manner as in Example 4-1, and the characteristics of the process release film were evaluated.
All of the reference examples were generally inferior in performance to the examples, and the ash adhesion test results were particularly inferior. Further, regarding the appearance, good results were not obtained except in Reference Example 4-1.

[Examples 4-10 to 4-17]
A process release film was prepared in the same manner as in Example 4-1, except that the films shown in Table 4-2 were changed to the release layers 4A and 4A ′ and the heat-resistant resin layer 4B in the combinations shown in Table 4-2. Then, sealing and releasing were performed, and the characteristics were evaluated.
As shown in FIG. 3a, the release film was placed between the upper mold and the lower mold in a state where a tension of 20N was applied, and then was vacuum-adsorbed on the parting surface of the upper mold. Next, after filling the substrate with sealing resin so as to cover the semiconductor chip, the semiconductor chip fixed to the substrate was placed in the lower mold and clamped. At this time, the temperature of the molding die (molding temperature) was 170 ° C., the molding pressure was 10 MPa, and the molding time was 100 seconds. Then, as shown in FIG. 3c, after sealing the semiconductor chip with a sealing resin, the resin-sealed semiconductor chip (semiconductor package) was released from the release film. The results are shown in Table 4-2.
In all the examples, despite the evaluation of the high temperature range at 170 ° C., the mold release property, the appearance of the molded product, and the mold followability are good in all the test items of the ash adhesion test, and are balanced from the viewpoint of performance. It was a release film for process. In particular, Examples 4-15 to 4-17 were process release films having good release properties, appearance of molded products, mold followability, and ash adhesion test results.

[Reference Examples 4-4 to 4-9]
A process release film was prepared in the same manner as in Examples 4-10 to 4-17 except that the film configuration shown in Table 4-2 was used, and sealing and release were performed to evaluate the characteristics. . The results are shown in Table 4-2.
In any of the reference examples, the performance generally did not reach that of each of the examples, and particularly, none of the molded products had good results in both the appearance and the ash adhesion test.

The details of each film described in Table 4-2 are the same as those described above for each film described in Table 4-1.
Details of the base materials 4B0g and 4B0h of the heat-resistant resin layer described only in Table 4-2 are as follows.
(4B0g) Biaxially stretched nylon film Biaxially stretched nylon film with a film thickness of 15 μm (product name: UNILON S330, manufactured by Idemitsu Unitech Co., Ltd.) (melting point: 221 ° C., heat of crystal melting: 60.3 J / g)
(4B0h) Biaxially stretched PET film Biaxially stretched PET film with a film thickness of 25 μm (manufactured by Teijin DuPont Films, product name: FT3PE) (melting point: 214 ° C., heat of crystal melting: 40.3 J / g)

The process release film of the first invention of the present application has a high level of releasability, suppression of wrinkles, and mold followability that could not be realized by the prior art. The technical effect of high value in practical use is that the molded product obtained by sealing etc. can be easily released and the molded product without appearance defects such as wrinkles and chips can be produced with high productivity. It has high availability in various fields of industries including the semiconductor process industry.
In addition, the process release film of the first invention of the present application can be used not only for semiconductor packages but also for various mold moldings in fiber reinforced plastic molding processes, plastic lens molding processes, etc. It has high applicability also in each field of the industry that performs mold forming.
The process release film of the second invention of the present application has a high level of mold release property, suppression of appearance defects, and mold followability that could not be realized by the prior art. By using this, a semiconductor chip or the like can be obtained. Molded products obtained by resin sealing can be easily released, and molded products with no appearance defects such as wrinkles, chips, and abnormal shapes (such as burrs and foreign matter adhesion) can be produced with high productivity. It has a technical effect of high value in practical use and has high applicability in various fields of industries including the semiconductor process industry.
In addition, the process release film of the second invention of the present application can be used not only for semiconductor packages but also for various mold moldings in fiber reinforced plastic molding processes, plastic lens molding processes, etc. It has high applicability also in each field of the industry that performs mold forming.
The process release film of the third invention of the present application has a high level of releasability, suppression of wrinkles, and mold followability that could not be realized by the prior art. The technical effect of high value in practical use is that the molded product obtained by sealing etc. can be easily released and the molded product without appearance defects such as wrinkles and chips can be produced with high productivity. It has high availability in various fields of industries including the semiconductor process industry.
In addition, the process release film according to the third invention of the present application can be used not only for semiconductor packages but also for various molds in fiber reinforced plastic molding processes, plastic lens molding processes, etc. It has high applicability also in each field of the industry that performs mold forming.
The process release film according to the fourth invention of the present application combines a high level of mold release, wrinkle suppression, and mold followability that could not be realized with the prior art. The technical effect of high value in practical use is that the molded product obtained by sealing etc. can be easily released and the molded product without appearance defects such as wrinkles and chips can be produced with high productivity. It has high availability in various fields of industries including the semiconductor process industry.
In addition, the process release film of the fourth invention of the present application can be used not only for semiconductor packages but also for various mold moldings in fiber reinforced plastic molding processes, plastic lens molding processes, etc. It has high applicability also in each field of the industry that performs mold forming.

1, 1-2, 1-3: Release film 2: Upper mold 3: Suction port 4: Sealing resin 4-2: Semiconductor package 5: Lower mold 6: Semiconductor chip 7: Substrate 8:

Mold

10, 20, 22: Release film 12: Heat-resistant resin layer 1B, 2B, 3B, 4B
14:

Adhesive layers

16, 16A: Release layers 1A, 2A, 3A, 4A
16B: Release layers 1A ′, 2A ′, 3A ′, 4A ′
24, 26: Roll 28: Mold 30: Upper mold 32: Lower mold 34: Semiconductor chip 34A: Substrate 36: Sealing resin 40, 44: Semiconductor package

Claims

A release film for process that is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction of the laminated film is 6% or less. 2. A release film for a process according to 1.
A release film for process that is a laminated film including a release layer 1A and a heat-resistant resin layer 1B,
The contact angle of the release layer 1A with respect to water is 90 ° to 130 °,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction of the laminated film is 7% or less. 3. A release film for a process according to 3.
The process release film according to any one of claims 1 to 4, wherein a rate of thermal dimensional change from 23 ° C to 120 ° C in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 1B is 6% or less. The process release film according to claim 5.
The process release film according to any one of claims 1 to 4, wherein a rate of thermal dimensional change from 23 ° C to 170 ° C in the transverse (TD) direction of the heat-resistant resin layer 1B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 1B is 4% or less. The process release film according to claim 7.
9. The release layer 1 A according to claim 1, comprising a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene-based resin. Release film for process.
The process release film according to any one of claims 1 to 9, wherein the heat resistant resin layer 1B comprises a stretched film.
The process release film according to claim 10, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
The heat amount of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat-resistant resin layer 1B is 15 J / g or more and 60 J / g or less. The release film for a process according to one item.
The laminated film further has a release layer 1A ′, and includes the release layer 1A, the heat-resistant resin layer 1B, and the release layer 1A ′ in this order,
The process release film according to any one of claims 1 to 12, wherein a contact angle of the release layer 1A 'with water is 90 ° to 130 °.
14. At least one of the release layer 1A and the release layer 1A ′ contains a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process as described in 2.
The process release film according to any one of claims 1 to 14, which is used for a sealing process with a thermosetting resin.
The process release film according to any one of claims 1 to 15, which is used in a semiconductor sealing process.
The process release film according to any one of claims 1 to 15, which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing the release film for a semiconductor sealing process according to any one of claims 1 to 14 on the inner surface of the molding die so that the release layer 1A faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
Disposing a release film for a semiconductor sealing process according to claim 13 or 14 on the inner surface of the molding die so that the release layer 1A 'faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A release film for process which is a laminated film including a release layer 2A and a heat resistant resin layer 2B,
The contact angle of the release film 2A of the laminated film with respect to water is 90 ° to 130 °, and the surface specific resistance value is 1 × 10 13 Ω / □ or less,
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the laminated film is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction of the laminated film is 6% or less. 21. A release film for process according to 20.
A release film for process which is a laminated film including a release layer 2A and a heat resistant resin layer 2B,
The contact angle of the release film 2A of the laminated film with respect to water is 90 ° to 130 °, and the surface specific resistance value is 1 × 10 13 Ω / □ or less,
The heat-resistant resin layer 2B includes a layer 2B1 containing a polymer antistatic agent,
The mold release film for a process as described above, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the laminated film is 4% or less.
The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction of the laminated film is 7% or less. The release film for a process according to 22.
24. The process separation according to any one of claims 20 to 23, wherein the heat-resistant resin layer 2B comprises a layer 2B1 containing a polymeric antistatic agent and an adhesive layer 2B2 containing an adhesive. Mold film.
The process release film according to any one of claims 20 to 24, wherein a thermal dimensional change rate from 23 ° C to 120 ° C in a transverse (TD) direction of the heat-resistant resin layer 2B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 2B is 6% or less. The release film for a process according to claim 25.
The process release film according to any one of claims 20 to 24, wherein a rate of thermal dimensional change from 23 ° C to 170 ° C in the transverse (TD) direction of the heat-resistant resin layer 2B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 2B is 4% or less. The process release film according to claim 27.
29. The release layer 2A according to any one of claims 20 to 28, wherein the release layer 2A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process.
The process release film according to any one of claims 20 to 29, wherein the heat resistant resin layer 2B comprises a stretched film.
The process release film according to claim 30, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
The heat amount of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat resistant resin layer 2B is 15 J / g or more and 60 J / g or less, any one of claims 20 to 31 The release film for a process according to one item.
The laminated film further has a release layer 2A ′, and includes the release layer 2A, the heat-resistant resin layer 2B, and the release layer 2A ′ in this order,
The process release film according to any one of claims 20 to 32, wherein a contact angle of the release layer 2A 'with water is 90 ° to 130 °.
34. The release film for process according to claim 33, wherein the surface specific resistance value of the release layer 2A ′ is 1 × 10 13 Ω / □ or less.
15. At least one of the release layer 2A and the release layer 2A ′ includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Or a release film for a process according to 15.
The process release film according to any one of claims 20 to 35, which is used for a sealing process with a thermosetting resin.
The process release film according to any one of claims 20 to 36, which is used in a semiconductor sealing process.
The process release film according to any one of claims 20 to 36, which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing the release film for semiconductor encapsulation process according to any one of claims 20 to 35 on the inner surface of the molding die so that the release layer 2A faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing the release film for semiconductor sealing process according to any one of claims 33 to 35 on the inner surface of the molding die so that the release layer 2A 'faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A release film for process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
The process release film according to claim 41, wherein a rate of thermal dimensional change from 23 ° C to 120 ° C in a transverse (TD) direction of the laminated film is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction of the laminated film is 6% or less. 43. A process release film according to 41 or 42.
A release film for process which is a laminated film including a release layer 3A and a heat-resistant resin layer 3B,
The contact angle of the release layer 3A with respect to water is 90 ° to 130 °,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
The process release film according to claim 44, wherein a thermal dimensional change rate from 23 ° C to 170 ° C in a transverse (TD) direction of the laminated film is 4% or less.
The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction of the laminated film is 7% or less. 46. A process release film according to 44 or 45.
The process release film according to any one of claims 41 to 46, wherein a thermal dimensional change rate from 23 ° C to 120 ° C in a transverse (TD) direction of the heat-resistant resin layer 3B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 3B is 6% or less. 48. A process release film according to claim 47.
The process release film according to any one of claims 41 to 46, wherein a thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction of the heat-resistant resin layer 3B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 3B is 5% or less. The release film for a process according to claim 49.
51. The release layer 3A according to any one of claims 41 to 50, wherein the release layer 3A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process.
The process release film according to any one of claims 41 to 51, wherein the heat-resistant resin layer 3B comprises a stretched film.
53. The process release film according to claim 52, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
54. The calorie of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat-resistant resin layer 3B is 20 J / g or more and 100 J / g or less. The release film for a process according to one item.
The laminated film further has a release layer 3A ′, and includes the release layer 3A, the heat-resistant resin layer 3B, and the release layer 3A ′ in this order,
The process release film according to any one of claims 41 to 54, wherein a contact angle of the release layer 3A 'with water is 90 ° to 130 °.
56. At least one of the release layer 3A and the release layer 3A ′ includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process as described in 2.
The process release film according to any one of claims 41 to 56, which is used for a sealing process with a thermosetting resin.
The process release film according to any one of claims 41 to 57, which is used in a semiconductor sealing process.
The process release film according to any one of claims 41 to 57, which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing the release film for a semiconductor sealing process according to any one of claims 41 to 56 on the inner surface of the molding die so that the release layer 3A faces the semiconductor device,
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing a release film for a semiconductor sealing process according to claim 55 or 56 on the inner surface of the molding die so that the release layer 3A ′ faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A release film for process which is a laminated film including a release layer 4A and a heat resistant resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 120 ° C. of 75 MPa to 500 MPa.
The process release film according to claim 62, wherein a thermal dimensional change rate from 23 ° C to 120 ° C in a transverse (TD) direction of the laminated film is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C to 120 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 120 ° C in the longitudinal (MD) direction of the laminated film is 6% or less. 62. A release film for a process according to 62 or 63.
A release film for process which is a laminated film including a release layer 4A and a heat resistant resin layer 4B,
The contact angle of the release layer 4A with respect to water is 90 ° to 130 °,
The heat-resistant resin layer 4B includes a layer 4B1 containing a polymer antistatic agent,
The release film for a process as described above, wherein the laminated film has a tensile elastic modulus at 170 ° C. of 75 MPa to 500 MPa.
The process release film according to claim 65, wherein a rate of thermal dimensional change from 23 ° C to 170 ° C in a transverse (TD) direction of the laminated film is 4% or less.
The sum of the thermal dimensional change rate from 23 ° C to 170 ° C in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C to 170 ° C in the longitudinal (MD) direction of the laminated film is 7% or less. 65. A release film for a process according to 65 or 66.
68. The process separation according to any one of claims 62 to 67, wherein the heat resistant resin layer 4B comprises a layer 4B1 containing a polymer antistatic agent and an adhesive layer 4B2 containing an adhesive. Mold film.
68. The process release film according to any one of claims 62 to 67, wherein the heat-resistant resin layer 4B comprises a layer 4B3 containing a polymer antistatic agent and an adhesive.
70. The process release film according to any one of claims 62 to 69, wherein a thermal dimensional change rate from 23 ° C. to 120 ° C. in a transverse (TD) direction of the heat-resistant resin layer 4B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 120 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 120 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 4B is 6% or less. 71. A process release film according to claim 70.
70. The process release film according to any one of claims 62 to 69, wherein a thermal dimensional change rate from 23 ° C. to 170 ° C. in a transverse (TD) direction of the heat resistant resin layer 4B is 3% or less.
The sum of the thermal dimensional change rate from 23 ° C. to 170 ° C. in the transverse (TD) direction and the thermal dimensional change rate from 23 ° C. to 170 ° C. in the longitudinal (MD) direction of the heat-resistant resin layer 4B is 5% or less. The process release film according to claim 72.
74. The release layer 4A according to any one of claims 62 to 73, wherein the release layer 4A includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process.
The process release film according to any one of claims 62 to 74, wherein the heat-resistant resin layer 4B comprises a stretched film.
The process release film according to claim 75, wherein the stretched film is selected from the group consisting of a stretched polyester film, a stretched polyamide film, and a stretched polypropylene film.
77. The calorie of crystal fusion in the first heating step measured by differential scanning calorimetry (DSC) according to JISK7221 of the heat resistant resin layer 4B is not less than 20 J / g and not more than 100 J / g. The release film for a process according to one item.
Surface resistivity is 1 × 10 13 Ω / □ or less, the process for release film according to any one of claims 62 77 of the releasing layer 4A.
The laminated film further has a release layer 4A ′, and includes the release layer 4A, the heat-resistant resin layer 4B, and the release layer 4A ′ in this order,
The process release film according to any one of claims 62 to 78, wherein a contact angle of the release layer 4A 'with water is 90 ° to 130 °.
80. At least one of the release layer 4A and the release layer 4A ′ includes a resin selected from the group consisting of a fluororesin, a 4-methyl-1-pentene (co) polymer, and a polystyrene resin. Release film for process as described in 2.
The process release film according to claim 79 or 80, wherein the release layer 4A 'has a surface resistivity of 1 x 10 13 Ω / □ or less.
The process release film according to any one of claims 62 to 81, which is used for a sealing process with a thermosetting resin.
83. A process release film according to any one of claims 62 to 82, which is used in a semiconductor sealing process.
83. A process release film according to any one of claims 62 to 82, which is used in a fiber-reinforced plastic molding process or a plastic lens molding process.
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
A step of disposing a release film for a semiconductor sealing process according to any one of claims 62 to 83 on the inner surface of the molding die so that the release layer 4A faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising:
A method of manufacturing a resin-encapsulated semiconductor,
Placing a semiconductor device to be resin-sealed at a predetermined position in a molding die; and
The step of disposing the release film for semiconductor sealing process according to any one of claims 79 to 81 on the inner surface of the molding die so that the release layer 4A 'faces the semiconductor device;
A step of injecting a sealing resin between the semiconductor device and the release film for semiconductor sealing process after clamping the molding die; and
A method for producing the resin-encapsulated semiconductor, comprising: