JP2012177084A - Heat-resistant temporary adhesive composition and heat-resistant temporary adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-resistant temporary adhesive composition; and to provide a heat-resistant temporary adhesive tape, which is used for temporarily fixing or protecting electric components, has high initial adhesive force to the electric components, has adhesive force required for fixation and protection, and is easily peeled off and removed without leaving adhesive deposit, wherein the adhesive force is less likely to degrade even if the adhesive tape is exposed to high temperature.SOLUTION: The heat-resistant temporary adhesive composition is used for temporarily fixing or protecting the electric components in a step of manufacturing the electric component. The adhesive composition contains, as materials for forming an adhesive layer 2 comprising the adhesive composition: an acrylic polymer; an energy ray polymerizable oligomer; a polymerization initiator; and a crosslinking agent. The acrylic polymer is a copolymer that has a repeating unit derived from acrylonitril.

Description

  The present invention relates to a heat-resistant temporary wearing pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape used for temporarily fixing or protecting the electronic component in a manufacturing process of the electronic component.

  Generally, adhesive tapes such as dicing tapes and back grind tapes are used in the manufacturing process of electronic components. Since these adhesive tapes are used for fixing and protecting parts, they have strong adhesive strength that can withstand environmental conditions in each manufacturing process, eliminating the need for fixing and protection. It is desirable that can be easily peeled off.

  As an adhesive tape having such properties, Patent Document 1 discloses one in which a radiation curable adhesive layer and an adhesive layer having a storage elastic modulus in a specific range are provided on one surface of a base film. ing. Patent Document 2 discloses a re-peelable pressure-sensitive adhesive composition comprising a water-affinity acrylic pressure-sensitive adhesive, an active energy ray-curable compound, a photopolymerization initiator, and a crosslinking agent. These show strong adhesive strength before irradiating with energy rays, etc., and fix and protect the adherend appropriately, but when irradiated with energy rays etc., the adhesive strength decreases significantly and can be easily peeled off from the adherend. It becomes that.

JP 2002-53819 A JP 2000-345131 A

  By the way, in recent years, in the manufacturing process of an electronic component, the component with the adhesive tape attached is often exposed to a high temperature. For this reason, the pressure-sensitive adhesive tape used in the manufacturing process of electronic components is also required to have heat resistance that can withstand high temperature conditions. However, the pressure-sensitive adhesive tape used to temporarily fix or protect the components has a low adhesive strength when exposed to high temperatures, and peels off during the process, or adheres firmly to the adherend after the process, There was a problem that adhesive residue was generated.

  The present invention has been made in view of the above problems, and is a heat-resistant temporary wearing pressure-sensitive adhesive composition and pressure-sensitive adhesive tape that are used for temporarily fixing or protecting an electronic component. It has high adhesive strength, and even when exposed to high temperatures, the adhesive strength is difficult to decrease, and has the adhesive strength necessary for fixing and protection. It aims at providing the adhesive composition and adhesive tape of the heat-resistant temporary wear which can be peeled.

  As a material for forming a heat-resistant temporary wearing pressure-sensitive adhesive composition, the present inventor has conducted extensive research to solve the above problems, and an acrylic polymer that is a copolymer having a repeating unit derived from acrylonitrile, By selecting an energy beam polymerizable oligomer, a polymerization initiator, and a cross-linking agent, even when exposed to high temperatures in a state of being affixed to an electronic component, the adhesive strength is unlikely to decrease, and In some cases, the present inventors have found that an adhesive tape that does not cause adhesive residue can be obtained, thereby completing the present invention.

  Specifically, the present invention provides the following.

  (1) The present invention is an adhesive composition for heat-resistant temporary wear used for temporarily fixing or protecting the electronic component in the manufacturing process of the electronic component, and includes an acrylic polymer and an energy beam polymerizable property. The pressure-sensitive adhesive composition includes an oligomer, a polymerization initiator, and a crosslinking agent, and the acrylic polymer is a copolymer having a repeating unit derived from acrylonitrile.

  (2) Moreover, this invention is the said adhesion with respect to the inorganic glass surface and silicon surface when an inorganic glass or a silicon plate and a heat resistant base material are laminated | stacked through the 10 micrometers adhesive layer which consists of the said adhesive composition. The adhesive layer has a 180 ° peeling adhesive strength (conforming to JIS Z0237) of 0.5 N / 25 mm or more after 20 minutes after the heat-resistant substrate is pasted on the inorganic glass surface and silicon surface, and 150 ° C. The pressure-sensitive adhesive composition according to (1), which is 0.5 N / 25 mm or more after being heated for 60 minutes and 0.4 N / 25 mm or less after being cured by irradiation with energy rays after the heating. It is.

  (3) Moreover, this invention is a polyethylene naphthalate film surface and a polyimide film surface when a polyethylene naphthalate film or a polyimide film and inorganic glass are laminated | stacked through the 10 micrometers adhesive layer which consists of the said adhesive composition. The adhesive layer has a 180 ° peel-off adhesive strength (based on JIS Z0237) of 0.3 N / 25 mm or more after 20 minutes have passed since the inorganic glass is pasted on the polyethylene naphthalate film surface and the polyimide film surface. Yes, after heating at 180 ° C. for 120 minutes, it is 0.5 N / 25 mm or more, and after curing by irradiation with energy rays after the heating, it is 0.3 N / 25 mm or less. It is an adhesive composition.

  (4) Moreover, this invention is an adhesive composition in any one of (1) to (3) containing an energy-beam polymerizable monomer.

  (5) Moreover, this invention is a heat-resistant temporary wearing adhesive tape in which the adhesive layer which consists of an adhesive composition in any one of said (1) to (4) is formed on the said heat resistant base material. is there.

  (6) Moreover, this invention is a heat-resistant temporary attachment adhesive tape as described in (5) whose heat shrinkage rate (JIS C2151 conformity) of the said heat resistant base material is 1.0% or less in MD direction and TD direction. is there.

  (7) Moreover, as for this invention, at least a 1st peeling film and a 2nd peeling film are through the adhesive layer which consists of an adhesive composition in any one of said (1) to (4). It is a laminated heat-resistant temporary wearing adhesive tape.

  (8) Moreover, as for this invention, the temporary attachment surface with the said adhesive layer in the said electronic component is an inorganic glass surface and / or a silicon surface, The heat-resistant temporary attachment adhesive tape as described in said (5) or (6) And the said to-be-adhered body formed by the said inorganic glass surface and / or silicon surface of the said electronic component being affixed through the said adhesive layer.

(9) Further, according to the present invention, the difference (Δysd) in the dispersion component of the surface free energy between the surface of the pressure-sensitive adhesive layer, the inorganic glass surface in contact with the surface of the pressure-sensitive adhesive layer, and the silicon surface is 11 mJ / m ² or more. It is the temporary adherend as described in (8).

  According to the heat-resistant temporary wearing pressure-sensitive adhesive composition and pressure-sensitive adhesive tape of the present invention, the initial pressure-sensitive adhesive force on electronic components is high, and even when exposed to high temperatures, the pressure-sensitive adhesive force is unlikely to decrease, for fixing and protection. The necessary adhesive force can be maintained, and further, when peeling and removing, it can be easily peeled without any adhesive residue.

It is sectional drawing which showed typically the adhesive tape which concerns on one Embodiment of this invention. It is sectional drawing which showed typically the adhesive tape which concerns on other embodiment of this invention.

  Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and may be implemented with appropriate modifications within the scope of the object of the present invention. be able to.

[Heat-resistant temporary adhesive composition]
The heat-resistant temporary wearing pressure-sensitive adhesive composition of the present invention is, for example, a pressure-sensitive adhesive composition used for temporarily fixing or protecting an electronic component having an inorganic glass surface and / or a silicon surface in the production process of the electronic component. It is. The pressure-sensitive adhesive composition of the present invention contains an acrylic polymer, an energy beam polymerizable oligomer, a polymerization initiator, and a crosslinking agent, and the acrylic polymer is a copolymer having a repeating unit derived from acrylonitrile. is there. In the present invention, an acrylic polymer that is a copolymer having a repeating unit derived from acrylonitrile, an energy ray polymerizable oligomer, a polymerization initiator, and a crosslinking agent are selected as a material for forming the pressure-sensitive adhesive layer. In addition, the initial adhesive strength to electronic parts is high, and even when exposed to high temperatures, the adhesive strength is difficult to decrease, maintaining the adhesive strength necessary for fixation and protection, and when peeling and removing It is significant that it was found for the first time that it can be easily peeled without remaining.

(Acrylic polymer)
The pressure-sensitive adhesive composition of the present invention contains, as a main ingredient, an acrylic polymer that is excellent in transparency, heat resistance, heat and humidity resistance, durability, suitability for coating, and the like and is low in cost. The acrylic polymer is not particularly limited as long as it is a copolymer having a repeating unit derived from acrylonitrile. For example, a copolymer of an acrylate ester and acrylonitrile, an acrylic ester, acrylonitrile, and other monomer And a copolymer with the body. Examples of the acrylic acid ester include ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, hydroxyl ethyl acrylate, propylene glycol acrylate, and glycidyl acrylate. These can be used alone or in combination of two or more. In the present invention, among the above acrylic esters, in particular, n-butyl acrylate and 2-ethylhexyl acrylate are excellent in transparency, heat resistance, moist heat resistance, durability, suitability for coating, etc., and at low cost. It is preferable in a certain point.

  Examples of other monomers include methyl acrylate, methyl methacrylate, styrene, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide, methacrylamide, glycidyl acrylate, Examples thereof include glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, n-ethylhexyl methacrylate and the like. These can be used alone or in combination of two or more. In the present invention, methyl methacrylate is preferable among the other monomers.

  In addition, other preferable monomers include, for example, copolymerizable hydroxyl group-containing monomers. In the present invention, the copolymerizable hydroxyl group-containing monomer refers to a monomer having a copolymerizable polymerizable group and a hydroxyl group in its structure. Examples of the copolymerizable hydroxyl group-containing monomer include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-chloro-2-hydroxypropyl acrylate, and polyethylene glycol acrylate. Of these, 2-hydroxyethyl acrylate is preferred in the present invention.

  In the pressure-sensitive adhesive composition of the present invention, the mass average molecular weight (Mw) of the acrylic polymer is preferably in the range of 150,000 to 1,500,000, and more preferably in the range of 400,000 to 1,200,000. . If it is in the said range, adjustment of the initial stage adhesive force of an adhesive layer is easy. In addition, it is possible to form a pressure-sensitive adhesive layer having a high cohesive force. The mass average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  In the pressure-sensitive adhesive composition of the present invention, the acrylic polymer has a repeating unit derived from acrylonitrile, and a desired cohesive force can be imparted to the pressure-sensitive adhesive layer by adjusting the ratio. The ratio of the repeating unit derived from acrylonitrile with respect to all repeating units of the acrylic polymer is preferably 3 to 40% by mass, more preferably 3 to 10% by mass, and 5 to 10% by mass. Even more preferred. If it is in the said range, even if it is a case where it exposes to high temperature, the adhesive force cannot fall easily and the adhesive layer which can maintain the adhesive force required for fixation and protection can be formed. In addition, when peeling and removing, adhesive residue hardly occurs.

(Energy beam polymerizable oligomer)
The pressure-sensitive adhesive composition of the present invention contains an energy beam polymerizable oligomer. The energy ray-polymerizable oligomer is not particularly limited as long as it can be polymerized by irradiation with energy rays, and examples thereof include oligomers such as photoradical polymerizability, photocationic polymerizability, and photoanion polymerizability. . Among these, a photo-radically polymerizable oligomer is preferable. This is because the curing speed is high, and a wide variety of compounds can be selected. Furthermore, physical properties such as adhesiveness before curing and peelability after curing can be easily controlled to desired ones. . Examples of the radical photopolymerizable oligomer include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyol (meth) acrylate, polyether (meth) acrylate, melamine (meth) acrylate, and silicone-based. (Meth) acrylate etc. are mentioned, and these may be used alone or in combination of two or more. Of these, polyurethane (meth) acrylate is preferred in the present invention.

  The mass average molecular weight (Mw) of the energy beam polymerizable oligomer is not particularly limited, but is preferably 250 to 5000, and more preferably 250 to 1500. If it is in the said range, a desired adhesive force will be shown before energy beam irradiation, and the adhesive layer which can peel easily can be formed, without adhesive residue remaining after energy beam irradiation. The weight average molecular weight is a value in terms of polystyrene when measured by gel permeation chromatography (GPC).

  The content of the energy beam polymerizable oligomer is preferably 10 to 60 parts by mass and more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the acrylic polymer. By adjusting the amount of the energy beam polymerizable oligomer, it is possible to control the adhesive strength after irradiation with the energy beam. If it exists in the said range, since the crosslinking density after energy beam irradiation will become sufficient, appropriate peelability can be implement | achieved. In addition, it is difficult for adhesive residue to adhere to the adherend due to a decrease in cohesive force.

  In addition to the energy beam polymerizable oligomer, an energy beam polymerizable monomer that can be polymerized by irradiation with energy rays may be contained. The energy ray polymerizable monomer is not particularly limited as long as it can be polymerized by irradiation with energy rays, similarly to the energy ray polymerizable oligomer. For example, monomers such as photoradical polymerizability, photocationic polymerizability, and photoanion polymerizability can be mentioned, the curing speed is fast, and it can be selected from a wide variety of compounds. A photo-radically polymerizable monomer that can easily control physical properties such as peelability after curing to a desired one is preferable. As the radical photopolymerizable monomer, a polyfunctional acrylate or a polyfunctional methacrylate is preferable. For example, trimethylol methane tri (meth) acrylate or trimethylol ethane tri having three or more (meth) acryloyl groups in one molecule. (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, these Of these, an ethylene oxide or a propylene oxide adduct is preferred. These have the function of curing the pressure-sensitive adhesive composition by three-dimensional crosslinking and reducing the adhesive strength when irradiated with ionizing radiation, and increasing the cohesive force of the pressure-sensitive adhesive so that it does not transfer to the adherend surface. It is because it has.

  When the energy ray polymerizable oligomer and the energy ray polymerizable monomer are contained in the pressure-sensitive adhesive composition, the total content is 10 to 60 parts by mass with respect to 100 parts by mass of the acrylic polymer. It is preferable and it is more preferable that it is 20-50 mass parts. By adjusting these total contents, it becomes possible to control the adhesive strength after irradiation with energy rays. If it exists in the said range, since the crosslinking density after energy beam irradiation will become sufficient, appropriate peelability can be implement | achieved. In addition, it is difficult for adhesive residue to adhere to the adherend due to a decrease in cohesive force.

  Examples of energy rays include rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, and infrared rays, electromagnetic waves such as X-rays and γ rays, electron beams, proton rays, and neutron rays. In view of the curing speed, the availability of the irradiation device, the price, etc., curing by ultraviolet irradiation is preferable.

(Polymerization initiator)
The pressure-sensitive adhesive composition of the present invention contains a polymerization initiator. According to the polymerization initiator, the sensitivity of the energy beam polymerizable oligomer and the energy beam polymerizable monomer can be increased, so that it is possible to reduce the polymerization curing time and energy beam irradiation amount by the energy beam. The polymerization initiator is not particularly limited, and preferred examples of commercially available products include IRGACURE184, IRGACURE754, IRGACURE2959, etc., manufactured by BASF Japan Ltd.

  The content of the polymerization initiator is not particularly limited as long as the radical chain reaction starts and proceeds, for example. Generally, the polymerization initiator is blended in such an amount that the absorbance at the maximum absorption wavelength of the polymerization initiator measured using a commercially available spectrophotometer is within the range of 0.4 to 0.5.

(Crosslinking agent)
The pressure-sensitive adhesive composition of the present invention contains a crosslinking agent. Since the pressure-sensitive adhesive composition of the present invention contains a crosslinking agent together with the acrylic polymer, the energy ray polymerizable oligomer, and the polymerization initiator, it has excellent heat resistance and is used in a situation where an electronic component is exposed to a high temperature. However, the adhesive strength does not decrease, and the adhesive strength necessary for fixing and protection is obtained. A crosslinking agent is not specifically limited, For example, an isocyanate type crosslinking agent, an epoxy-type crosslinking agent, etc. are mentioned. As an isocyanate type crosslinking agent, for example, a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having a terminal isocyanate group obtained by reacting a polyisocyanate compound and a polyol compound, 3 of the urethane prepolymer Examples include a polymer. Examples of the polyisocyanate compound include 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4′-diisocyanate, 3 -Methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, lysine isocyanate and the like.

  Examples of the epoxy-based crosslinking agent include sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, neopentyl glycol diester. Examples include polyfunctional epoxy compounds such as glycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutadiene diglycidyl ether.

  The crosslinking agent can be used alone or in combination of two or more, and may be appropriately selected according to the type of the acrylic polymer. For example, when the monomer constituting the acrylic polymer contains a copolymerizable hydroxyl group-containing monomer, an isocyanate-based crosslinking agent is preferable, and when a copolymerizable carboxyl group-containing monomer is contained, an epoxy-based polymer is used. A crosslinking agent is preferred. Here, the copolymerizable carboxyl group-containing monomer means a monomer having a copolymerizable polymerizable group and a carboxyl group in its structure, for example, acrylic acid, methacrylic acid, carboxyethyl (meth). Examples include acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, and crotonic acid. According to the above selection, it is possible to form a pressure-sensitive adhesive layer that is less likely to cause a decrease in adhesive strength when exposed to high temperatures.

  In addition, as a commercial item of the said isocyanate type crosslinking agent, L-45 (made by Soken Chemical Co., Ltd.), TD-75 (made by Soken Chemical Co., Ltd.), BXX5627 (made by Toyo Ink Manufacturing Co., Ltd.), X-301, for example. -422SK (manufactured by Seiden Chemical Co., Ltd.) or the like can be suitably used. Moreover, as a commercial item of the said epoxy-type crosslinking agent, E-5XM (made by Soken Chemical Co., Ltd.), E-5C (made by Soken Chemical Co., Ltd.) etc. can be used suitably, for example.

  Although content of a crosslinking agent changes with kinds of crosslinking agent, in the case of an isocyanate type crosslinking agent, for example with respect to a total of 100 mass parts of the said acrylic polymer and the said energy-beam polymerizable oligomer, it is set to 0. It is preferable that it is 01-15 mass parts, and it is more preferable that it is 0.01-10 mass parts. If it is the said range, the adhesiveness of an adhesive layer and a base material can be improved. When less than 0.01 parts by mass, the adhesiveness between the pressure-sensitive adhesive layer and the substrate becomes insufficient, or it becomes difficult for the pressure-sensitive adhesive layer to have sufficient strength, and when it peels from the adherend In some cases, the pressure-sensitive adhesive layer causes cohesive failure to cause adhesive residue. If it exceeds 15 parts by mass, it remains as an unreacted monomer in the pressure-sensitive adhesive layer, and the cohesive force may be reduced.

  Moreover, in the case of an epoxy-type crosslinking agent, it is preferable that it is 0.01-15 mass parts with respect to a total of 100 mass parts of the said acrylic polymer and the said energy-beam polymerizable oligomer, 0.01-10 More preferably, it is part by mass. If it is the said range, the adhesive force and cohesion force before energy ray irradiation can be controlled to desired intensity | strength. If it is less than 0.01 parts by mass, it is difficult for the pressure-sensitive adhesive layer to have sufficient strength, and the pressure-sensitive adhesive layer may cause cohesive failure when peeled off from the adherend, resulting in adhesive residue. If it exceeds 15 parts by mass, the adhesive strength before irradiation with energy rays is reduced, and thus it may be difficult to appropriately fix and protect the electronic component.

  In addition, the pressure-sensitive adhesive composition of the present invention includes a silane coupling agent, a tackifier, a metal chelating agent, a surfactant, an antioxidant, and an ultraviolet absorber as long as the object of the present invention is not impaired. Various additives such as pigments, dyes, colorants, antistatic agents, preservatives, antifoaming agents, and wettability adjusting agents can be blended.

[Method for producing pressure-sensitive adhesive composition for heat-resistant temporary wear]
The manufacturing method of the heat-resistant temporary wearing adhesive composition of this invention is not specifically limited, A conventionally well-known method can be used. For example, it can be produced by dissolving or dispersing the acrylic polymer, the energy beam polymerizable oligomer, the polymerization initiator, the crosslinking agent, and, if necessary, the various additives in an organic solvent. Although it does not specifically limit as an organic solvent, For example, toluene, methyl ethyl ketone, ethyl acetate, dimethylacetamide, these mixed solutions, etc. can be used conveniently.

[Heat-resistant temporary wearing adhesive tape]
The heat-resistant temporary wearing pressure-sensitive adhesive tape (hereinafter, also referred to as pressure-sensitive adhesive tape) of the present invention is a heat-resistant temporary wearing pressure-sensitive adhesive tape used for temporarily fixing or protecting the electronic component in the manufacturing process of the electronic component. The pressure-sensitive adhesive tape according to one embodiment of the present invention is a pressure-sensitive adhesive comprising a pressure-sensitive adhesive composition containing an acrylic polymer, an energy beam polymerizable oligomer, a polymerization initiator, and a crosslinking agent on a heat-resistant substrate. A layer is formed, and the acrylic polymer is a copolymer having repeating units derived from acrylonitrile. And the adhesive layer currently formed in the adhesive tape which concerns on one Embodiment of this invention has 180 degree peeling adhesive force (JIS Z0237 conformity) with respect to an inorganic glass surface and a silicon surface on the said inorganic glass surface and a silicon surface. After 20 minutes have elapsed since pasting, it is 0.5 N / 25 mm or more, and after heating at 150 ° C. for 60 minutes, it is 0.5 N / 25 mm or more, and after curing by irradiation with energy rays after the heating. Then, it is 0.4 N / 25 mm or less. In the present invention, an acrylic polymer that is a copolymer having a repeating unit derived from acrylonitrile, an energy ray polymerizable oligomer, a polymerization initiator, and a crosslinking agent are selected as a material for forming the pressure-sensitive adhesive layer. In addition, the initial adhesive force on the inorganic glass surface and silicon surface of the electronic component is high, and even when exposed to high temperatures, the adhesive force is difficult to decrease, maintaining the adhesive force necessary for fixing and protection, It is significant that it has been found for the first time that a pressure-sensitive adhesive tape that can be easily peeled off without leaving adhesive residue is obtained.

  Moreover, the adhesive tape which concerns on other embodiment of this invention laminates | stacks at least a 1st peeling film and a 2nd peeling film through the adhesive layer which consists of said adhesive composition. And the adhesive layer currently formed in the adhesive tape which concerns on other embodiment of this invention attaches the said inorganic glass to the polyethylene naphthalate film surface and the polyimide film surface, and 0.3N / It is 25 mm or more, 0.5 N / 25 mm or more after heating at 180 ° C. for 120 minutes, and 0.3 N / 25 mm or less after curing by irradiation with energy rays after the heating. The present invention is characterized in that both sides of the pressure-sensitive adhesive layer are bonded together with a release film, whereby when a hard plate member such as an inorganic glass plate or polycarbonate is used as the base material, the pressure-sensitive adhesive layer is used as the base material. It can be transferred to an adhesive layer support, and the degree of freedom of the adhesive layer support can be extended not only to a soft substrate but also to a hard plate member.

  First, the structure of the adhesive tape which concerns on one Embodiment of this invention is demonstrated using FIG. FIG. 1 is a cross-sectional view schematically showing an adhesive tape 10 according to an embodiment of the present invention. In FIG. 1, the pressure-sensitive adhesive tape 10 has a pressure-sensitive adhesive layer 2 and a release layer 3 sequentially formed on a substrate 1, but is not limited thereto. Hereinafter, the substrate 1, the pressure-sensitive adhesive layer 2, the release layer 3, and the pressure-sensitive adhesive tape 10 will be described in this order.

<Substrate 1>
In the adhesive tape 10 of the present invention, a base material 1 having heat resistance is used. In the present invention, the base material 1 having heat resistance refers to a base material having a melting point higher than 120 ° C. that can withstand use at an assumed heating temperature (120 ° C.) in a manufacturing process of an electronic component. A base material having a melting point higher than 180 ° C. is preferable. Moreover, in the adhesive tape 10 of this invention, it is preferable that the base material 1 has a heat shrinkage rate (JIS C2151 conformity, 150 degreeC * 30min) of 1.0% or less in both MD and TD, and 0.5% or less. More preferably. Furthermore, the base material 1 is preferably a base material that does not hinder the transmission of energy rays and has the necessary strength and flexibility. For example, a polyester resin, a polyvinyl chloride resin, a fluorine resin, a polystyrene resin, Synthetic resins made from known resins such as (meth) acrylic resins, cellulose resins, polycarbonate resins, polyimide resins, polyolefin resins, polyvinyl alcohol resins, polyimide resins, phenol resins, polyurethane resins, etc. A film is mentioned. These can be used alone or in combination of two or more. Moreover, the base material 1 may be a single layer or a laminate of two or more layers. From the viewpoint of mechanical strength, a uniaxially stretched or biaxially stretched film is preferred. Since the adhesive tape of the present invention is used to temporarily fix or protect an electronic component in the manufacturing process of the electronic component, the heat resistance, dimensional stability, energy ray permeability, flexibility, strength, etc. In addition, it is preferable to use a polyester-based resin that is also excellent in rigidity, extensibility, stackability, and chemical resistance.

  Examples of the polyester-based resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyarylate, polytetramethylene terephthalate, etc. Among them, polyethylene that is easy to handle and inexpensive Terephthalate is particularly preferred.

  Although the thickness of the base material 1 is not specifically limited, It is preferable that it is 30-300 micrometers, and it is more preferable that it is 50-100 micrometers. If it is the said range, since the form of the adhesive tape 10 can be maintained, workability | operativity, such as sticking and peeling of the adhesive tape 10, is good. In addition, since warp, slack, breakage and the like hardly occur and sufficient mechanical strength is exhibited, it is also possible to supply and process in a continuous belt shape. Furthermore, in the manufacturing process of the electronic component, it is possible to appropriately protect the surface of the electronic component that is the adherend. If the thickness exceeds the above-mentioned thickness, excessive performance may increase the cost.

  In addition, when using a light ray as an energy ray, it is preferable that the transmittance | permeability with respect to a 400 nm or less light ray of a base material is 80% or more. The light transmittance can be measured using a commercially available spectrophotometer, for example, MPC2200 manufactured by Shimadzu Corporation.

  The formation method of the base material 1 is not specifically limited, For example, conventionally well-known film forming methods, such as a solution casting method, a melt extrusion method, and a calendar method, can be used. Moreover, you may use the commercially available base material previously formed into a film form by the said method.

  In addition, in order to improve the wettability with the adhesive composition, the substrate 1 is subjected to corona treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, vapor deposition treatment, alkali treatment, etc. on one side or both sides. You may give a well-known easy-adhesion process.

<Adhesive layer 2>
In the pressure-sensitive adhesive tape 10 of the present invention, the pressure-sensitive adhesive layer 2 made of the pressure-sensitive adhesive composition is formed on the heat-resistant substrate 1. The thickness of the pressure-sensitive adhesive layer 2 is usually 5 to 50 μm, preferably 10 to 30 μm. If it is in the said range, adhesive physical property will be stabilized. If the thickness is less than 5 μm, sufficient adhesive strength may not be obtained. If the thickness exceeds 50 μm, the energy rays cannot be sufficiently transmitted to the inside of the pressure-sensitive adhesive layer 2, and the adhesive strength is increased by irradiation of the energy rays. May not decrease. In addition, excessive performance may increase costs.

  When the 10 μm-thick adhesive layer 2 made of the above-mentioned adhesive composition is formed on the heat-resistant substrate 1 having a thickness of 50 μm, the adhesive layer 2 peels off 180 ° from the inorganic glass surface and the silicon surface. (According to JIS Z0237) is 0.5 N / 25 mm or more after 20 minutes have elapsed after pasting to the inorganic glass surface and silicon surface, and 0.5 N / 25 mm or more after heating at 150 ° C. for 60 minutes. And 0.4 N / 25 mm or less after curing by irradiation with energy rays after the heating, preferably 0.7 N / 25 mm after 20 minutes have passed after pasting the inorganic glass surface or silicon surface. Above, after heating at 150 ° C. for 60 minutes, it is 0.7 N / 25 mm or more, and after curing by irradiation with energy rays after the heating, 0.3 N / 25 mm or less A. In addition, said heating conditions are an example of the heating conditions added on the manufacturing process of an electronic component.

  If it is within the above range, the initial adhesive force on the inorganic glass surface and silicon surface of the electronic component is sufficiently high, and it does not peel from the adherend even under high temperature conditions during the manufacturing process of the electronic component, Furthermore, when peeling and removing, it can be easily peeled without any adhesive residue.

In the pressure-sensitive adhesive tape 10 of the present invention, the difference in the surface free energy dispersion component (Δysd) between the surface of the pressure-sensitive adhesive layer 2 and the inorganic glass surface and silicon surface in contact with the surface of the pressure-sensitive adhesive layer 2 is 11 mJ / m ² or more. It is preferable that it is 13 mJ / m ² or more. When the difference in the surface free energy dispersion component between the surface of the pressure-sensitive adhesive layer 2 and the surface of the inorganic glass and the silicon surface in contact with the surface of the pressure-sensitive adhesive layer 2 is 11 mJ / m ² or more, when exposed to high temperatures It is difficult to cause a decrease in adhesive strength, and it can be easily peeled off when irradiated with energy rays after heating.

  In addition, the dispersion component of the surface free energy of the surface of the pressure-sensitive adhesive layer 2 and the inorganic glass surface and the silicon surface in contact with the surface of the pressure-sensitive adhesive layer 2 is first determined by the contact angles of ethylene glycol, water, and methylene iodide. Using a contact angle meter, measurement is performed by a method in accordance with JIS K2396. And it analyzes from the obtained value and the theory of Kitazaki-Hata. As the contact angle meter, for example, a FACE contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd. can be used.

<Peeling layer 3>
The pressure-sensitive adhesive tape 10 of the present invention preferably has a release layer 3. The release layer 3 means a release sheet made of a release member having peelability and having a function of protecting the surface of the pressure-sensitive adhesive layer 2. The release member is not particularly limited as long as it has the required strength and flexibility, and generally a synthetic resin film subjected to silicone release treatment is used. As a material for the synthetic resin film, for example, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyarylate, polytetramethylene terephthalate are preferable. Although the thickness of the peeling layer 3 is not specifically limited, Preferably it is 25-100 micrometers.

  Then, the structure of the adhesive tape which concerns on other embodiment of this invention is demonstrated using FIG. FIG. 2 is a cross-sectional view schematically showing an adhesive tape 20 according to another embodiment of the present invention. In FIG. 2, the pressure-sensitive adhesive tape 20 has the release layer 3 formed on both surfaces of the pressure-sensitive adhesive layer 2. In contrast to the adhesive tape 10 according to one embodiment, the difference is that the substrate 1 of the adhesive tape 10 is replaced with a release layer 3. As a result, it is not limited to the base material 1 of the adhesive tape 10, and for example, a hard plate member such as inorganic glass can be used as the support base material.

  When an adhesive layer 2 having a thickness of 10 μm made of the above-mentioned adhesive composition is formed on an inorganic glass having a thickness of 900 μm, the adhesive layer 2 is peeled off by 180 ° from the polyethylene naphthalate film surface and the polyimide film surface. (According to JIS Z0237) is 0.3N / 25 mm or more after 20 minutes have passed since the inorganic glass is pasted on the polyethylene naphthalate film surface and polyimide film surface, and after heating at 180 ° C. for 120 minutes 0.5 N / 25 mm or more, and 0.3 N / 25 mm or less after curing by irradiation with energy rays after the heating.

  If it is within the above range, the initial adhesive strength to the electronic component is sufficiently high, and it does not peel off from the adherend even under high temperature conditions during the manufacturing process of the electronic component. Can be easily peeled off without leaving adhesive residue.

[Production method of heat-resistant temporary wearing adhesive tape 10, 20]
The manufacturing method of the adhesive tapes 10 and 20 of the present invention is not particularly limited, and a conventionally known method can be used. For example, in the case of the heat-resistant temporary wearing pressure-sensitive adhesive tape 10 according to one embodiment, the pressure-sensitive adhesive composition is entirely coated on the heat-resistant substrate 1 with an applicator or the like to form the pressure-sensitive adhesive layer 2. On the other hand, in the case of the heat-resistant temporary wearing pressure-sensitive adhesive tape 20 according to another embodiment, the pressure-sensitive adhesive composition is entirely coated on the release layer 3 with an applicator or the like to form the pressure-sensitive adhesive layer 2. Then, the adhesive tape 2 of the present invention can be formed by drying the adhesive layer 2 and laminating a peelable synthetic resin film or the like.

  The method for coating the pressure-sensitive adhesive composition on the heat-resistant substrate 1 or the release layer 3 is not particularly limited, and a conventionally known method can be used. Examples of the forming method by printing include a gravure printing method, a flexographic printing method, and an offset printing method. Examples of the coating method include roll coating, reverse coating, comma coating, knife coating, die coating, and gravure coating.

  Although the thickness of the adhesive tapes 10 and 20 of this invention is not specifically limited, It is preferable that it is 80-350 micrometers, and it is more preferable that it is 90-140 micrometers. If it is the said range, since it has moderate softness | flexibility, handling becomes easy.

  The sticking target of the adhesive tapes 10 and 20 of the present invention is, for example, an electronic component having an inorganic glass surface and / or a silicon surface, and includes an electronic component made of inorganic glass or silicon. According to the pressure-sensitive adhesive tapes 10 and 20 of the present invention, the initial pressure-sensitive adhesive force on the inorganic glass surface and the silicon surface is high, and even when exposed to high temperatures, the pressure-sensitive adhesive force hardly decreases, and is necessary for fixing and protection. Adhesive strength, and when peeling and removing, it is easy to peel off without leaving glue by a simple operation of irradiating energy rays, so appropriate fixing and protection are required during the process Finally, it is suitable as a tape for an electronic component manufacturing process that involves use under high-temperature conditions for peeling and removing. Specifically, it is suitable as an adhesive tape used for temporarily fixing or protecting components in a printed wiring board manufacturing process. Examples of the component include an electronic component used for manufacturing an IC chip.

  As a usage method of the adhesive tape 10 which concerns on one Embodiment of this invention, the following method is mentioned, for example. First, the adhesive tape 10 of the present invention is attached to the inorganic glass surface and / or the silicon surface of the electronic component to be attached. Then, through the steps of heat treatment, processing, chemical treatment, etc., when there is no need for fixing or protection, the adhesive layer 2 is cured by irradiating energy rays such as ultraviolet rays from the substrate side of the adhesive tape. Thus, the adhesive tape is peeled off from the inorganic glass surface and / or silicon surface of the electronic component.

  As a usage method of the adhesive tape 20 which concerns on other embodiment of this invention, the following method is mentioned, for example. First, one release layer 3 is peeled off, and the pressure-sensitive adhesive layer 2 may be transferred onto the support substrate in advance. After that, it is stuck and fixed to, for example, a polyethylene naphthalate (PEN) film surface and / or a polyimide (PI) film surface of an electronic component to be attached. Then, through the steps of heat treatment, processing, chemical treatment, etc., when there is no need for fixing or protection, the adhesive layer 2 is cured by irradiating energy rays such as ultraviolet rays from the substrate side of the adhesive tape. Thus, the substrate 1 is peeled and removed from the PEN surface and / or PI surface of the electronic component.

When using ultraviolet rays as energy rays, for example, using a high-pressure mercury lamp, ultrahigh-pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, etc. Irradiation may be performed so as to be 50 mJ / cm ² or more, preferably 200 mJ / cm ² or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention does not receive a restriction | limiting at all by these description.

<Example 1>
Acrylic adhesive (trade name: E-306, acrylic polymer + energy beam polymerizable oligomer + energy beam polymerizable monomer + polymerization initiator, acrylic polymer: n-butyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate Copolymer with acrylonitrile, mass ratio of constituent monomers: n-butyl acrylate + methyl methacrylate + 2-hydroxyethyl acrylate / acrylonitrile (95/5), mass average molecular weight of acrylic polymer: about 650,000, energy beam polymerizable oligomer : Polyurethane acrylate oligomer, energy beam polymerizable monomer: dipentaerythritol triacrylate, polymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF) (Product name: L-45, isocyanate-based crosslinking agent, solid content 45%, manufactured by Soken Chemical Co., Ltd.) 5 parts by mass, mixed solvent of toluene and methyl ethyl ketone (product name: KT11, mass ratio 1: 1, DIC) The product was diluted with 87 parts by mass of Graphics Co., Ltd. and sufficiently dispersed to prepare a coating solution for forming an adhesive layer.

  Next, the base material (biaxially stretched polyester film, trade name: Lumirror S56, heat shrinkage (conforming to JIS C2151, 150 ° C. × 30 min): MD is 0.5%, TD is 0.3%, film thickness: 50 μm, The pressure-sensitive adhesive layer forming coating solution was coated on the entire surface with an applicator so that the film thickness after drying was 10 μm. Then, it was made to dry and the peeling sheet (PET separator, brand name: SP-PET-01, film thickness: 38 micrometers, Mitsui Chemicals Tosero Co., Ltd.) was laminated, and the adhesive tape of Example 1 was obtained.

<Example 2>
Acrylic adhesive (trade name: E-306, acrylic polymer + energy beam polymerizable oligomer + energy beam polymerizable monomer + polymerization initiator, acrylic polymer: n-butyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate Copolymer with acrylonitrile, mass ratio of constituent monomers: n-butyl acrylate + methyl methacrylate + 2-hydroxyethyl acrylate / acrylonitrile (95/5), mass average molecular weight of acrylic polymer: about 650,000, energy beam polymerizable oligomer : Polyurethane acrylate oligomer, energy beam polymerizable monomer: dipentaerythritol triacrylate, polymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF) (Trade name: L-45, isocyanate-based crosslinking agent, solid content 45%, manufactured by Soken Chemical Co., Ltd.) 10 parts by mass, mixed solvent of toluene and methyl ethyl ketone (trade name: KT11, mass ratio 1: 1, DIC The product was diluted with 87 parts by mass of Graphics Co., Ltd. and sufficiently dispersed to prepare a coating solution for forming an adhesive layer.

  Subsequently, on the release sheet (PET separator, trade name: SP-PET-01, film thickness: 38 μm, manufactured by Mitsui Chemicals, Inc.), the pressure-sensitive adhesive layer is formed so that the film thickness after drying is 10 μm. The entire surface of the coating liquid was applied with an applicator to form an adhesive layer. Then, it was made to dry and the said peeling sheet was laminated, and the adhesive tape of Example 2 was obtained.

<Comparative Example 1>
Acrylic adhesive (trade name: N-4498, acrylic polymer + energy beam polymerizable oligomer, acrylic polymer: copolymer of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and (meth) acrylic acid , Acrylic polymer mass average molecular weight: about 400,000, energy ray polymerizable oligomer: polyurethane acrylate oligomer, solid content: 40%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 100 parts by mass, a polymerization initiator (trade name: IRGACURE754) , Photo radical generator, solid content: 100%, manufactured by BASF Japan Ltd.) 1.4 parts by mass and crosslinking agent (trade name: Coronate L, isocyanate-based crosslinking agent, solid content: 75%, manufactured by Nippon Polyurethane Co., Ltd. ) 1.5 parts by mass, toluene and methyl ethyl ketone Except that it was diluted with 180 parts by mass of a mixed solvent (trade name: KT11, mass ratio 1: 1, manufactured by DIC Graphics Co., Ltd.) and sufficiently dispersed to prepare a coating solution for forming an adhesive layer. A pressure-sensitive adhesive tape of Comparative Example 1 was obtained in the same manner as in Example 1.

<Comparative example 2>
Acrylic adhesive (trade name: N-7257, acrylic polymer + energy ray polymerizable oligomer, acrylic polymer: copolymer of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and (meth) acrylic acid , Acrylic polymer mass average molecular weight: about 400,000, energy ray polymerizable oligomer: polyurethane acrylate oligomer, solid content: 41%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 100 parts by mass, a polymerization initiator (trade name: IRGACURE754) , Photo radical generator, solid content: 100%, manufactured by BASF Japan Ltd.) 1.4 parts by mass and crosslinking agent (trade name: Coronate L, isocyanate-based crosslinking agent, solid content: 75%, manufactured by Nippon Polyurethane Co., Ltd. ) 2 parts by mass, toluene and methyl ethyl ketone Except for diluting with 186 parts by mass of a mixed solvent (trade name: KT11, mass ratio 1: 1, manufactured by DIC Graphics Co., Ltd.) and sufficiently dispersing to prepare a coating solution for forming an adhesive layer. 1 was used to obtain a pressure-sensitive adhesive tape of Comparative Example 2.

<Comparative Example 3>
Acrylic adhesive (trade name: SK Dyne SW-2B, acrylic polymer: copolymer of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate and (meth) acrylic acid, mass average molecular weight of acrylic polymer : About 200,000, solid content 45%, manufactured by Soken Chemical Co., Ltd. 100 parts by mass, energy ray polymerizable oligomer (trade name: UV-7600B, polyurethane acrylate oligomer, solid content: 100%, Nippon Synthetic Chemical Industry Co., Ltd.) 12 parts by mass, a polymerization initiator (trade name: IRGACURE184, photoradical generator, solid content: 100%, manufactured by BASF Japan Ltd.), 1.3 parts by mass, and a crosslinking agent (trade name: E-5XM, Epoxy-based crosslinking agent, solid content: 5%, manufactured by Soken Chemical Co., Ltd. 7 parts by mass and crosslinking agent (trade name: L-4 5, isocyanate crosslinking agent, solid content 45%, 2.7 parts by mass of Nippon Polyurethane Co., Ltd.), mixed solvent of toluene and methyl ethyl ketone (trade name: KT11, mass ratio 1: 1, DIC Graphics) Manufactured) A pressure-sensitive adhesive tape of Comparative Example 3 was obtained in the same manner as in Example 1 except that it was diluted with 100 parts by mass and sufficiently dispersed to prepare a pressure-sensitive adhesive layer-forming coating solution.

<Comparative example 4>
Acrylic adhesive (trade name: SK Dyne SW-2B, acrylic polymer: copolymer of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate and (meth) acrylic acid, mass average molecular weight of acrylic polymer : About 200,000, solid content 45%, manufactured by Soken Chemical Co., Ltd. 100 parts by mass, energy ray polymerizable oligomer (trade name: UV-7600B, polyurethane acrylate oligomer, solid content: 100%, Nippon Synthetic Chemical Industry Co., Ltd.) 12 parts by mass, a polymerization initiator (trade name: IRGACURE184, photoradical generator, solid content: 100%, manufactured by BASF Japan Ltd.), 1.3 parts by mass, and a crosslinking agent (trade name: E-5XM, Epoxy-based crosslinking agent, solid content: 5%, manufactured by Soken Chemical Co., Ltd. 7 parts by mass and crosslinking agent (trade name: L-4 5, isocyanate-based crosslinking agent, solid content 45%, manufactured by Nippon Polyurethane Co., Ltd.) 7 parts by mass, mixed solvent of toluene and methyl ethyl ketone (trade name: KT11, mass ratio 1: 1, manufactured by DIC Graphics) A pressure-sensitive adhesive tape of Comparative Example 4 was obtained in the same manner as in Example 1 except that it was diluted with 100 parts by mass and sufficiently dispersed to prepare a pressure-sensitive adhesive layer-forming coating solution.

<Comparative Example 5>
Acrylic adhesive (trade name: E-306, acrylic polymer + energy beam polymerizable oligomer + energy beam polymerizable monomer + polymerization initiator, acrylic polymer: n-butyl acrylate, methyl methacrylate and 2-hydroxyethyl acrylate Copolymer with acrylonitrile, mass ratio of constituent monomers: n-butyl acrylate + methyl methacrylate + 2-hydroxyethyl acrylate / acrylonitrile (95/5), mass average molecular weight of acrylic polymer: about 650,000, energy beam polymerizable oligomer : Polyurethane acrylate oligomer, energy beam polymerizable monomer: dipentaerythritol triacrylate, polymerization initiator: 1-hydroxy-cyclohexyl-phenyl-ketone) 100 parts by mass, toluene and methyl Except for diluting with 87 parts by mass of a mixed solvent of tilketone (trade name: KT11, mass ratio 1: 1, manufactured by DIC Graphics Co., Ltd.) and sufficiently dispersing to prepare a coating solution for forming an adhesive layer, A pressure-sensitive adhesive tape of Comparative Example 5 was obtained in the same manner as in Example 1.

<Comparative Example 6>
Acrylic adhesive (trade name: N-4498, acrylic polymer + energy beam polymerizable oligomer, acrylic polymer: copolymer of n-butyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, and (meth) acrylic acid , Acrylic polymer mass average molecular weight: about 400,000, energy ray polymerizable oligomer: polyurethane acrylate oligomer, solid content: 40%, manufactured by Nippon Synthetic Chemical Industry Co., Ltd. 100 parts by mass, a polymerization initiator (trade name: IRGACURE754) , Photo radical generator, solid content: 100%, manufactured by BASF Japan Ltd.) 1.4 parts by mass, mixed solvent of toluene and methyl ethyl ketone (trade name: KT11, mass ratio 1: 1, DIC Graphics Corporation) Manufactured) Dilute with 180 parts by mass and disperse thoroughly , Except that to prepare a pressure-sensitive adhesive layer forming coating solution, in the same manner as in Example 1 to obtain a pressure-sensitive adhesive tape of Comparative Example 6.

[Adhesive strength evaluation]
About the adhesive tape obtained in the said Examples 1, 2 and Comparative Examples 1-6, adhesive force evaluation with respect to inorganic glass and a silicon wafer was performed.

(Measurement of surface free energy)
First, the surface free energy was measured about the inorganic glass (brand name: float plate glass, Nihon Takuto Co., Ltd.) and silicon (silicon wafer) used for adhesive strength evaluation. The surface free energy is measured by using a contact angle meter (product name: FACE contact angle meter CA-D type, manufactured by Kyowa Interface Science Co., Ltd.) as a measuring device, in accordance with JIS R3257, ethylene glycol, water, and iodide. The contact angle of methylene was measured, and the surface free energy was calculated by analyzing the dispersion component, the polar component, and the hydrogen bonding component from the measured value and the Kitazaki-Hata theory. The results are shown in Table 1.

  About the surface of the adhesive layer of the adhesive tape obtained in the said Examples 1, 2 and Comparative Examples 1-4, the surface free energy was measured. The test piece was prepared by cutting an adhesive tape into a width of 25 mm and a length of 100 mm. Then, the release sheet of the test piece is peeled off, and the contact angle of the surface of the pressure-sensitive adhesive layer is measured by the same method as described above. From the measured value and the Kitazaki-Hata theory, the dispersion component, the polar component, and the hydrogen bond The components were analyzed and the surface free energy was calculated. The results are shown in Table 2.

(Measurement of arithmetic average roughness)
Arithmetic average roughness (Ra) was measured for inorganic glass (trade name: float plate glass, manufactured by Nippon Tact Co., Ltd.) and silicon (silicon wafer) used for adhesive strength evaluation. The arithmetic average roughness (Ra) was measured by a method based on JIS B0601-2001. The measurement conditions are shown below. As a result, the arithmetic average roughness (Ra) of the inorganic glass was 0.17 μm, and the arithmetic average roughness (Ra) of silicon was 0.14 μm.

<Measurement conditions>
Equipment used: Atomic force microscope (Product name: NanoScope V MultiMode, probe: MPP-11100-10, manufactured by Veeco)
Used scanner: J-scanner
Measurement mode: TM-AFM
Scanning range: 1.0 × 1.0μm
Resolution: 1024 × 1024
Scan rate: 0.5 Hz

(Initial adhesion measurement)
About the adhesive tape obtained in the said Example 1 and Comparative Examples 1-6, the peeling sheet of the said test piece was peeled off, it laminated using the roller of 2 kg with respect to each of the said inorganic glass and silicon | silicone, and normal temperature normal humidity Left under for 20 minutes. About the adhesive tape obtained in the said Example 2, after peeling off one peeling sheet and transferring an adhesive layer on inorganic glass, peeling off the other peeling sheet, and with respect to each of two types of adherends Lamination was performed using a 2 kg roller. And it was left to stand under normal temperature normal humidity for 20 minutes. Thereafter, for each adhesive tape, the initial adhesive strength was measured using a universal material testing machine (model 5565, manufactured by Instron Japan) (compliant with JIS Z0237, peeling speed: 300 mm / min, peeling distance: 50 mm, peeling) (Angle: 180 °). The results for inorganic glass are shown in Table 3, and the results for silicon are shown in Table 4. Table 5 shows the results of the two types of adherends.

The two types of adherends laminated on the adhesive tape obtained in Example 2 are as follows.
(1) Polyethylene naphthalate film, product name: Q51, manufactured by Teijin DuPont Films, Ltd. (2) Polyimide film, product name: Kapton 200H, manufactured by Toray DuPont Co., Ltd.

The evaluation criteria for initial adhesive strength are as follows.
[Example 1 and Comparative Examples 1-6]
○: 0.5 N / 25 mm or more, x: less than 0.5 N / 25 mm.
[Example 2]
○: 0.3 N / 25 mm or more, x: less than 0.3 N / 25 mm.

(Measurement of adhesive strength after heat treatment)
About the adhesive tape obtained in the said Example 1 and Comparative Examples 1-6, the peeling sheet of the said test piece was peeled off, it laminated using the roller of 2 kg with respect to each of the said inorganic glass and silicon | silicone, and normal temperature normal humidity Left under for 20 minutes. About the adhesive tape obtained in the said Example 2, after peeling off one peeling sheet and transferring an adhesive layer on inorganic glass, peeling off the other peeling sheet, and with respect to each of two types of adherends Lamination was performed using a 2 kg roller. And it was left to stand under normal temperature normal humidity for 20 minutes. Next, the pressure-sensitive adhesive tape obtained in Example 1 and Comparative Examples 1 to 6 was heated at 150 ° C. for 60 minutes, and the pressure-sensitive adhesive tape obtained in Example 2 was heated at 180 ° C. for 120 minutes. Using an all-purpose material testing machine (model 5565, manufactured by Instron Japan), the adhesive strength after heat treatment was measured (according to JIS Z0237, peeling speed: 300 mm / min, peeling distance: 50 mm, peeling angle: 180 °). )did. The results for inorganic glass are shown in Table 3, and the results for silicon are shown in Table 4. Table 5 shows the results of the polyethylene naphthalate film and the polyimide film.

  In addition, the evaluation criteria of the adhesive force after heat processing are as follows. ○: 0.5 N / 25 mm or more, x: less than 0.5 N / 25 mm.

(Measurement of adhesive strength after UV irradiation)
About the adhesive tape obtained in the said Example 1 and Comparative Examples 1-6, the peeling sheet of the said test piece was peeled off, it laminated using the roller of 2 kg with respect to each of the said inorganic glass and silicon | silicone, and normal temperature normal humidity The mixture was allowed to stand for 20 minutes under heating and then heated at 150 ° C. for 60 minutes. About the adhesive tape obtained in the said Example 2, after peeling off one peeling sheet and transferring an adhesive layer on inorganic glass, peeling off the other peeling sheet, and with respect to each of two types of adherends Lamination was performed using a 2 kg roller. And after standing for 20 minutes under normal temperature and normal humidity, it heated at 180 degreeC for 120 minutes. Next, after irradiating ultraviolet rays (integrated light amount: 200 mj / cm ² ) using a fusion H / bulb lamp as a light source from the base material side, a universal material testing machine (5565 type, manufactured by Instron Japan) was used. Then, the adhesive strength after ultraviolet irradiation was measured (according to JIS Z0237, peeling speed: 300 mm / min, peeling distance: 50 mm, peeling angle: 180 °). The results for inorganic glass are shown in Table 3, and the results for silicon are shown in Table 4. Table 5 shows the results of the polyethylene naphthalate film and the polyimide film.

  In addition, the evaluation criteria of the adhesive force after ultraviolet irradiation are as follows. ○: 0.4 N / 25 mm or less, ×: more than 0.4 N / 25 mm.

[Check for adhesive residue]
About the adhesive tape obtained in the said Examples 1, 2 and Comparative Examples 1-6, the presence or absence of the adhesive residue with respect to inorganic glass and silicon | silicone was confirmed. First, the adhesive tape was cut into a width of 25 mm and a length of 100 mm to prepare a test piece. Next, for the adhesive tapes obtained in Example 1 and Comparative Examples 1 to 6, the release sheet of the test piece was peeled off and laminated using a 2 kg roller for each of the inorganic glass and silicon, After leaving at room temperature and normal humidity for 20 minutes, it was heated at 150 ° C. for 60 minutes. On the other hand, for the pressure-sensitive adhesive tape obtained in Example 2, after peeling off one release sheet and transferring the pressure-sensitive adhesive layer onto the inorganic glass, the other release sheet was peeled off to each of the two types of adherends. On the other hand, lamination was performed using a 2 kg roller. And after standing for 20 minutes under normal temperature and normal humidity, it heated at 180 degreeC for 120 minutes. Next, after irradiating ultraviolet rays (integrated light quantity: 500 mj / cm ² ) from the base material side using an H • bulb lamp manufactured by Fusion as a light source, the test piece was peeled off (peeling speed: 300 mm / min, peeling distance: 50 mm, (Peeling angle: 180 °), the adhesive residue (width 1 mm or more) on the surface of the inorganic glass and silicon was confirmed with an optical microscope (VHX-600, manufactured by Keyence Corporation, magnification 200). The results for inorganic glass are shown in Table 3, and the results for silicon are shown in Table 4. Table 5 shows the results of the polyethylene naphthalate film and the polyimide film.

As shown in Tables 3 and 4, the pressure-sensitive adhesive tapes of Examples 1 and 2 showed good initial pressure-sensitive adhesive force, and even when heat-treated, the pressure-sensitive adhesive force did not decrease, and it was easy to remove and remove. The peelable adhesive strength was shown. Further, no adhesive residue was generated after peeling.
In contrast, the pressure-sensitive adhesive tapes of Comparative Examples 1 to 6 did not decrease in adhesive strength after heat treatment or to such an extent that they could be easily peeled even when irradiated with ultraviolet rays.

  From the results shown in Tables 1 to 4, the difference (Δysd) in the dispersion component of the surface free energy between the inorganic glass surface and the silicon surface in contact with the surface of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape is the adhesive strength and UV after the heat treatment. It is presumed to be related to the adhesive strength after irradiation.

DESCRIPTION OF SYMBOLS 1 Base material 2 Adhesive layer 3 Peeling layer 10,20 Adhesive tape

Claims (9)

A heat-resistant temporary adhesive composition used for temporarily fixing or protecting the electronic component in the manufacturing process of the electronic component,
Contains an acrylic polymer, an energy beam polymerizable oligomer, a polymerization initiator, and a crosslinking agent,
The pressure-sensitive adhesive composition, wherein the acrylic polymer is a copolymer having a repeating unit derived from acrylonitrile.   180 ° of the pressure-sensitive adhesive layer relative to the inorganic glass surface and the silicon surface when inorganic glass or a silicon plate and a heat-resistant substrate having a thickness of 50 μm are laminated through a pressure-sensitive adhesive layer of 10 μm made of the pressure-sensitive adhesive composition. Peeling adhesive strength (based on JIS Z0237) is 0.5 N / 25 mm or more after 20 minutes have passed since the heat-resistant substrate is pasted on the inorganic glass surface and silicon surface, and heated at 150 ° C. for 60 minutes. 2. The pressure-sensitive adhesive composition according to claim 1, which is 0.5 N / 25 mm or more after being cured and 0.4 N / 25 mm or less after curing by irradiation with energy rays after the heating.   180 ° pulling of the pressure-sensitive adhesive layer with respect to the polyethylene naphthalate film surface and the polyimide film surface when a polyethylene naphthalate film or a polyimide film and an inorganic glass are laminated through a 10 μm pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition Peeling adhesive strength (according to JIS Z0237) is 0.3 N / 25 mm or more after 20 minutes after the inorganic glass is pasted on the polyethylene naphthalate film surface and polyimide film surface, and heated at 180 ° C. for 120 minutes. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is 0.5 N / 25 mm or more after being cured and 0.3 N / 25 mm or less after curing by irradiation with energy rays after the heating.   The pressure-sensitive adhesive composition according to any one of claims 1 to 3, comprising an energy ray polymerizable monomer.   A heat-resistant temporary wearing pressure-sensitive adhesive tape in which a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition according to claim 1 is formed on the heat-resistant substrate.   The heat-resistant temporary wearing pressure-sensitive adhesive tape according to claim 5, wherein the heat-shrinkable substrate has a heat shrinkage ratio (conforming to JIS C2151) of 1.0% or less in the MD direction and TD direction.   A heat-resistant temporary wearing adhesive tape in which at least a first release film and a second release film are laminated via an adhesive layer comprising the adhesive composition according to any one of claims 1 to 4.   The temporary attachment surface with the said adhesive layer in the said electronic component is an inorganic glass surface and / or a silicon surface, The heat-resistant temporary attachment adhesive tape of Claim 5 or 6, the said inorganic glass surface of the said electronic component, and / or Or the to-be-adhered body in which a silicon surface is stuck through the said adhesive layer. The surface difference of the surface free energy ((DELTA) ysd) of the surface of the said adhesive layer, and the inorganic glass surface and silicon surface which contact | connects the surface of the said adhesive layer is 11 mJ / m < ² > or more. Temporary body.

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