JP5332419B2 - Photosensitive adhesive composition, film adhesive, adhesive sheet, adhesive pattern, semiconductor wafer with adhesive layer, semiconductor device, and method for manufacturing semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive adhesive composition which is excellent in patterning ability by the use of an alkali developing liquid, has satisfactory thermo-compression adhesiveness even after patterning, is excellent in heat resistance after adhesion and is also excellent in low-temperature pasting ability when the adhesive composition is formed into a film shape. <P>SOLUTION: The photosensitive adhesive composition comprising an alkali-soluble resin (A), a dihydropyridine derivative (B) and an epoxy resin (C) is molded into a film-like adhesive 1, wherein a flow amount when the film-like adhesive is compressed at 0.2 MPa for 60 sec while being heated at 180&deg;C is at least 200 &mu;m. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a photosensitive adhesive composition, a film adhesive and an adhesive sheet using the composition, an adhesive pattern, a semiconductor wafer with an adhesive layer, a semiconductor device, and a method for manufacturing the semiconductor device.

  In the manufacture of a semiconductor device such as a semiconductor package, an adhesive is conventionally used for joining a semiconductor element and a support base for mounting a semiconductor element. This adhesive is required to have heat resistance and moisture resistance reliability for ensuring sufficient solder reflow resistance from the viewpoint of the reliability of the semiconductor device. In addition, there is a method of bonding through a process of applying a film-like adhesive to a semiconductor wafer or the like, and in this case, low-temperature application property is required in order to reduce thermal damage to the adherend.

  In recent years, as electronic components have been improved in performance and functionality, semiconductor packages having various forms have been proposed. Depending on a method for simplifying the function, form, and assembly process of a semiconductor device, the above characteristics may be obtained. In addition, an adhesive having a pattern forming ability is required. A photosensitive adhesive having a photosensitive function is known as an adhesive pattern.

  Photosensitivity is a function in which a portion irradiated with light is chemically changed and insolubilized or solubilized in an aqueous solution or an organic solvent. When this photosensitive photosensitive adhesive is used, a high-definition adhesive pattern can be formed by exposing through a photomask and forming a pattern with a developer.

As a material constituting the photosensitive adhesive having such a pattern forming function, a material based on a polyimide resin precursor (polyamide acid) or a polyimide resin has been used so far in consideration of heat resistance. (For example, refer to Patent Documents 1 to 5).
JP 2000-290501 A JP 2001-329233 A JP-A-11-024257 Japanese Patent Application Laid-Open No. 06-043648 JP 2000-035668 A

  However, the above materials are excellent in heat resistance. However, when the former polyamic acid is used, at the time of thermal ring-closing imidization, and when the latter polyimide resin is used, it is preferably 250 ° C. or more during processing. Requires a high temperature of 300 ° C. or higher, so that there are problems such as damage to the adherend and other constituent materials due to moisture generated at the time of thermal ring closure, large thermal damage to peripheral members, and easy generation of thermal stress. there were.

  On the other hand, when imparting thermocompression bonding after pattern formation, it is important to ensure sufficient fluidity during heating with respect to the adherend in order to ensure the performance as an adhesive. If the above-mentioned fluidity during heat is not sufficient, there is a high possibility that the moisture resistance reliability and the reflow resistance are lowered due to insufficient adhesion to the adherend. Therefore, in such a photosensitive adhesive used for bonding between adherends such as semiconductor elements and semiconductor elements, glass, organic substrates, etc., or bonding to a substrate having unevenness, heat to the adherends is used. Good thermal fluidity is required after pattern formation so as to ensure press-bondability.

  Here, when polyamic acid is used, in order to avoid damage to the adherend and other constituent materials due to moisture generated at the time of thermal ring closure, a method of thermal ring-closing imidization before pressure-bonding the adherend is also conceivable. However, the polyimide obtained by this method has a high glass transition temperature, and when it contains a thermosetting component, it reacts during thermal ring-closing imidization, so it does not flow sufficiently during pressure bonding with the adherend, and low temperature processing There is a problem that the property, adhesiveness, embedding property, etc. are greatly impaired. Therefore, it was difficult to contain other thermosetting components, and it was difficult to express sufficient adhesive force. Furthermore, even in the above method, there is a problem that damage to the substrate due to thermal ring closure at a high temperature is large.

  In addition, low temperature processing is achieved by blending an adhesive containing a polyimide resin with a thermoplastic resin having a relatively low Tg and a reduced molecular weight, a photocurable monomer such as (meth) acrylate, and a thermosetting resin. Attempts have also been made to improve solderability and solder heat resistance. However, in such a method, a cross-linking reaction is used for pattern formation, and the fluidity during heating is greatly impaired. Therefore, both the pattern formability with an alkali developer and the ability to stick to an adherend at a low temperature. At the same time, it was difficult to achieve a high level.

  In addition, the above-mentioned conventional materials are difficult to impart good re-adhesiveness that can express sufficiently high adhesive force when thermocompression-bonded after exposure, and sufficient re-thermocompression after exposure. It was difficult to achieve both properties and sufficiently high adhesion after curing. Furthermore, when the above conventional material is subjected to a pattern formation and pressure-bonded to the adherend and then subjected to a heat treatment, unreacted components are volatilized and tend to cause peeling of the adherend and / or element contamination.

  Therefore, it has low temperature sticking property, pattern forming ability, and secures hot fluidity that enables thermocompression bonding under the above-mentioned conditions of low temperature, low pressure and short time, and high temperature including reflow resistance. Materials that can achieve both adhesion and low outgassing, and their design are not yet sufficient. Therefore, in order to develop a material that can achieve both of the above-mentioned various characteristics, further detailed or precise material design is required.

  Therefore, the present invention is excellent in pattern formability with an alkaline developer, has sufficient thermocompression bonding after pattern formation, has excellent heat resistance after adhesion (that is, adhesiveness at high temperature), and is formed into a film. A photosensitive adhesive composition excellent in low-temperature adhesiveness, a film-like adhesive using the same, an adhesive sheet, an adhesive pattern, a semiconductor wafer with an adhesive layer, a semiconductor device, and manufacture of the semiconductor device It aims to provide a method.

  The present invention is a photosensitive adhesive composition containing (A) an alkali-soluble resin, (B) a dihydropyridine derivative, and (C) an epoxy resin, which is formed into a film and then heated to 180 ° C. while being heated. Provided is a photosensitive adhesive composition having a flow amount of 200 μm or more when pressed at 2 MPa for 60 seconds.

Here, the flow amount is measured on a test piece obtained by cutting an adhesive layer made of the photosensitive resin composition on a PET substrate so as to have a thickness of 50 μm ± 5 μm into a size of 10 mm × 10 mm. Is done. That is, the test piece is sandwiched between two slide glasses (manufactured by MATSANAMI, 76 mm × 26 mm × 1.0 to 1.2 mm thickness) with a PET substrate, and the whole is placed on a 180 ° C. hot platen. The average value of the amount of protrusion of the adhesive layer from the four sides of the PET base material after heating and pressurizing for 60 seconds by applying a load of ² kgf / cm ² (0.2 MPa) while heating is the flow amount. And The protruding amount of the adhesive layer means the distance from the extreme end portion of the protruding adhesive layer to the PET substrate and can be measured by observation using an optical microscope.

  The present invention also provides a photosensitive adhesive composition comprising (A) an alkali-soluble resin, (B) a dihydropyridine derivative and (C) an epoxy resin, wherein (A) the glass transition temperature of the alkali-soluble resin is −20. A photosensitive resin composition having a temperature of ˜140 ° C. is provided.

  According to the photosensitive adhesive composition of the present invention, by having the above-described configuration, it is possible to achieve pattern formation by an alkali developer and low-temperature thermocompression bonding after pattern formation at a high level. It has excellent heat resistance afterwards, and when it is formed into a film, excellent low temperature sticking property can be obtained.

  In the photosensitive adhesive composition of the present invention, the (A) alkali-soluble resin is preferably a resin having a carboxyl group and / or a hydroxyl group, and the resin having a carboxyl group and / or a hydroxyl group is a polyimide. It is more preferable. In this case, the adhesiveness and heat resistance after curing can be further improved.

  Here, the polyimide resin is preferably a polyimide resin obtained by reacting a tetracarboxylic dianhydride with a diamine having a carboxyl group and / or a hydroxyl group in the molecule.

  The polyimide resin is obtained by reacting tetracarboxylic dianhydride with an aromatic diamine represented by the following structural formula (I) and / or an aromatic diamine represented by the following structural formula (II). It is preferable that it is a polyimide resin. Thereby, the pattern formation property by an alkali developing solution can be improved further.

  Moreover, from the viewpoint of improving the adhesiveness after curing, the photosensitive adhesive composition of the present invention preferably further comprises (D) a compound having two or more phenolic hydroxyl groups in the molecule.

  Moreover, the compound which has a 2 or more phenolic hydroxyl group in the said (D) molecule | numerator can further improve the adhesiveness after hardening, if the compound represented by following structural formula (IV) is included.

  In the photosensitive adhesive composition of the present invention, the (C) epoxy resin preferably contains a compound represented by the following structural formula (III).

  Moreover, this invention provides the film adhesive formed by forming the said photosensitive adhesive composition in a film form. Such a film-like adhesive is composed of the photosensitive adhesive composition of the present invention, and therefore has a pattern forming property with an alkali developer, a thermocompression bonding property after pattern formation, a heat resistance property after adhesion, and a low temperature sticking property. Everything can be achieved at a high level.

  Moreover, this invention provides an adhesive sheet provided with a base material and the adhesive bond layer which is provided on the one surface of this base material and consists of the said photosensitive adhesive composition. Since such an adhesive sheet is provided with an adhesive layer made of the photosensitive adhesive composition of the present invention, pattern formability with an alkali developer, thermocompression bonding after pattern formation, heat resistance after adhesion, and low temperature application All of sex can be achieved at a high level. In addition, it is easy to handle, contributing to the efficiency of the semiconductor device assembly process.

  In the present invention, an adhesive layer composed of the above photosensitive adhesive composition is formed on an adherend, the adhesive layer is exposed through a photomask, and the exposed adhesive layer is exposed to an alkaline aqueous solution. To provide an adhesive pattern formed by development processing. By forming the adhesive pattern of the present invention from the photosensitive adhesive composition according to the present invention, it is possible to achieve high definition and excellent adhesiveness, and excellent heat resistance after bonding. And moisture resistance reliability can be obtained.

  The present invention also provides a semiconductor wafer with an adhesive layer, comprising a semiconductor wafer and an adhesive layer formed on one surface of the semiconductor wafer and made of the photosensitive adhesive composition. Such a semiconductor wafer with an adhesive layer is provided with an adhesive layer made of the photosensitive adhesive composition of the present invention, so that excellent low-temperature sticking property can be obtained, contributing to the efficiency of the semiconductor device assembly process.

  Moreover, this invention provides the semiconductor device by which a semiconductor element and the supporting member for semiconductor element mounting are adhere | attached using the said photosensitive adhesive composition. Such a semiconductor device has a photosensitive adhesive composition according to the present invention in which a semiconductor element and a supporting member for mounting a semiconductor element are excellent in pattern formability, thermocompression bonding after pattern formation, heat resistance after adhesion, and low-temperature sticking property. Therefore, it is possible to sufficiently cope with the simplification of the manufacturing process and to have excellent reliability.

  The present invention further provides a method for manufacturing a semiconductor device, comprising the step of bonding a semiconductor element and an adherend (supporting member for mounting a semiconductor element) using the photosensitive adhesive composition. According to these semiconductor device manufacturing methods, since the photosensitive adhesive composition of the present invention is used, a semiconductor device having excellent reliability can be provided.

  According to the present invention, the pattern formability with an alkali developer and the thermocompression bondability after pattern formation can be achieved at a high level, and further, the film has excellent heat resistance after bonding and is formed into a film. Can provide a method for forming a photosensitive adhesive composition, a film adhesive, and an adhesive pattern that are also excellent in low-temperature sticking property. Moreover, according to this invention, the adhesive sheet which can contribute to efficiency improvement of a semiconductor device assembly process, the semiconductor wafer with an adhesive bond layer, the semiconductor device excellent in reliability, and the manufacturing method of a semiconductor device can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios. In addition, “(meth) acrylate” in the present specification means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.

  The photosensitive adhesive composition of the present invention contains at least (A) an alkali-soluble resin, (B) a dihydropyridine derivative, and (C) an epoxy resin, and is heated to 180 ° C. after being formed into a film shape. However, the flow amount when pressurized for 60 seconds at 0.2 MPa is 200 μm or more.

  Moreover, the photosensitive adhesive composition of the present invention contains (A) an alkali-soluble resin, (B) a dihydropyridine derivative and (C) an epoxy resin, and the glass transition temperature of the (A) alkali-soluble resin is as follows. -20 to 140 ° C.

<(A) component>
Examples of the alkali-soluble resin (A) constituting the photosensitive adhesive composition according to the present invention include an alkali-soluble group, specifically, a thermoplastic resin having a carboxyl group and / or a hydroxyl group. Such thermoplastic resins include polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, polyurethaneimide resins, polyurethaneamideimide resins, siloxane polyimide resins, polyesterimide resins or copolymers thereof or precursors thereof. Phenoxy resin, polybenzoxazole resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyester resin, polyether ketone resin, (meth) acrylic copolymer having a weight average molecular weight of 10,000 to 1,000,000. Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.

  Moreover, as (A) alkali-soluble resin, the resin which has a carboxyl group is preferable at the point from which favorable developability is acquired. Furthermore, (A) the alkali-soluble resin is preferably a resin having an alkali-soluble group at the terminal or side chain. Moreover, when an alkali-soluble group is a hydroxyl group, a phenolic hydroxyl group is preferable.

  The application temperature of the film adhesive of the present invention to the wafer back surface is preferably 20 to 200 ° C, more preferably 20 to 150 ° C, more preferably 25 to 100 from the viewpoint of suppressing warpage of the semiconductor wafer. It is still more preferable that it is ° C. In order to enable application at the above temperature, the glass transition temperature (Tg) of the film adhesive is preferably 150 ° C. or lower. Therefore, Tg of (A) alkali-soluble resin used for a photosensitive adhesive composition is -20-140 degreeC, it is preferable that it is 0-120 degreeC, and it is more preferable that it is 30-100 degreeC. (A) If the Tg of the alkali-soluble resin exceeds 140 ° C., there is a high possibility that the application temperature to the wafer back surface will exceed 200 ° C., and warpage due to thermal stress at the time of bonding to the wafer back surface is likely to occur. If the Tg is less than −20 ° C., the tackiness of the film surface in the B stage state becomes too strong, and the handleability tends to deteriorate. When determining the composition of the polyimide resin described below, it is preferable to design the Tg to be 140 ° C. or lower, and more preferably to be 120 ° C. or lower.

  Moreover, it is preferable that the weight average molecular weight of (A) alkali-soluble resin is controlled within the range of 10000-300000, It is more preferable that it is 10000-100000, It is still more preferable that it is 10000-80000. When the weight average molecular weight is in the above range, the strength, flexibility and tackiness when the photosensitive adhesive composition is made into a sheet or film are good, and the heat fluidity is good. Therefore, it is possible to ensure a good embedding property in the wiring step on the substrate surface. If the weight average molecular weight is less than 10,000, the film formability tends to be poor, and if it exceeds 300,000, the fluidity during heating tends to be poor and the embedding property to the unevenness on the substrate tends to be lowered. Further, (A) the solubility of the alkali-soluble resin in an alkaline developer is lowered, and the pattern forming property tends to be lowered due to the lowered developability.

  (A) By setting the Tg and the weight average molecular weight of the alkali-soluble resin within the above ranges, not only can the temperature of application to the backside of the wafer be kept low, but also the semiconductor element is adhered and fixed to the semiconductor element mounting support member. The heating temperature (die bonding temperature) at the time can also be lowered, and an increase in warpage of the semiconductor element can be suppressed. Moreover, the fluidity | liquidity at the time of die bonding and the developability which are the characteristics of this invention can be provided effectively.

  In addition, said Tg is the main dispersion peak temperature when (A) alkali-soluble resin is formed into a film, and a temperature rising rate is obtained using a viscoelasticity analyzer “RSA-2” (trade name) manufactured by Rheometrics. Measurement was performed under the conditions of 5 ° C./min, frequency 1 Hz, measurement temperature −150 to 300 ° C., the tan δ peak temperature in the vicinity of Tg was measured, and this was defined as the main dispersion temperature. Moreover, the said weight average molecular weight is a weight average molecular weight when measured in polystyrene conversion using the high performance liquid chromatography "C-R4A" (brand name) by Shimadzu Corporation.

  Moreover, it is preferable that (A) alkali-soluble resin is a polyimide resin at the point of heat resistance and adhesiveness. The polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method. That is, in the organic solvent, tetracarboxylic dianhydride and diamine are equimolar, or if necessary, the total amount of diamine is preferably 0.00 with respect to the total 1.0 mol of tetracarboxylic dianhydride. The composition ratio is adjusted in the range of 5 to 2.0 mol, more preferably 0.8 to 1.0 mol (the order of addition of each component is arbitrary), and the addition reaction is performed at a reaction temperature of 80 ° C. or lower, preferably 0 to 60 ° C. . As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. In addition, in order to suppress the fall of the various characteristics of an adhesive composition, it is preferable that the said tetracarboxylic dianhydride is what recrystallized and refined with acetic anhydride.

  In addition, about the composition ratio of the tetracarboxylic dianhydride and diamine in the said condensation reaction, when the total of diamine exceeds 2.0 mol with respect to the total 1.0 mol of tetracarboxylic dianhydride, the polyimide obtained There exists a tendency for the quantity of the amine terminal polyimide oligomer to increase in resin, and when the weight average molecular weight of a polyimide resin becomes small, there exists a tendency for the various characteristics including the heat resistance of adhesive composition to fall. On the other hand, if the total amount of diamines is less than 0.5 mol, the amount of acid-terminated polyimide oligomer tends to increase, the weight average molecular weight of the polyimide resin decreases, and various properties including the heat resistance of the adhesive composition Tends to decrease.

  Moreover, it is preferable to determine suitably the composition ratio of preparation of tetracarboxylic dianhydride and diamine so that the weight average molecular weight of the polyimide resin obtained may be 10000-300000.

  The polyimide resin can be obtained by dehydrating and ring-closing the reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method in which heat treatment is performed and a chemical ring closure method using a dehydrating agent.

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracar Acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3, 6, 7- Trachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6-tetracarboxylic dianhydride Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) Methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1, 3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2 , 3,4-Butanetetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7- Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic acid Dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2 , 2]-Oct -7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3 4-dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) ) Phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic acid) Anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuran) L) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic dianhydride represented by the following general formula (VI) Is mentioned.

（式中、ｎは２〜２０の整数を示す）

(In the formula, n represents an integer of 2 to 20)

  The tetracarboxylic dianhydride represented by the general formula (VI) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, specifically 1,2- (ethylene) bis. (Trimellitic anhydride), 1,3- (trimethylene) bis (trimellitic anhydride), 1,4- (tetramethylene) bis (trimellitic anhydride), 1,5- (pentamethylene) bis (trimellitic anhydride), 1,6- (hexamethylene) bis (trimellitic anhydride), 1,7- (heptamethylene) bis (trimellitic anhydride), 1,8- (octamethylene) bis (trimellitic anhydride), 1,9- ( Nonamethylene) bis (trimellitic anhydride), 1,10- (decamethylene) bis (trimellitic anhydride), 1,12- (dodecame) Ren) bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), and 1,18 (octadecamethylene) bis (trimellitate anhydride) is

  The tetracarboxylic dianhydride is preferably a tetracarboxylic dianhydride represented by the following formula (VII) or (VIII) from the viewpoint of imparting good solubility in a solvent and moisture resistance reliability.

  The above tetracarboxylic dianhydrides can be used singly or in combination of two or more.

  The diamine used as a raw material for the polyimide resin preferably includes an aromatic diamine represented by the following formulas (I) and (II). The diamine represented by the following formulas (I) and (II) is preferably 1 to 50 mol% of the total diamine. Thereby, a polyimide resin soluble in an alkali developer can be prepared.

  There is no restriction | limiting in particular as other diamine used as a raw material of the said polyimide resin, For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'- diaminodiphenyl ether, 3,4'-diaminodiphenyl ether 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis (4-amino-3,5-dimethylphenyl) methane, bis ( 4-amino-3,5-diisopropylphenyl) methane, 3,3′-diaminodiphenyldifluoromethane, 3,4′-diaminodiphenyldifluoromethane, 4,4′-diaminodiphenyldifluoromethane, 3,3′-diaminodiphenyl Sulfo 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 3,3 ′ -Diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2 '-(3,4'-diaminodiphenyl) Propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2 -Bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) Benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,3 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 3 , 4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- ( 3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminophenoxy) phenyl) sulfide, bis (4- (4-aminophenoxy) phenyl) sulfide, bis (4- (3- Aromatic diamines such as aminophenoxy) phenyl) sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,5-diaminobenzoic acid, , 3-bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, the following general formula (IX), the aliphatic ether diamine represented by the following general formula (XI), the following general formula ( And siloxane diamines represented by XII).

［式中、Ｑ^１、Ｑ^２及びＱ^３は、各々独立に炭素数１〜１０のアルキレン基を示し、ｍ_１は２〜８０の整数を示す。］

[Wherein, Q ¹ , Q ² and Q ³ each independently represents an alkylene group having 1 to 10 carbon atoms, and m ₁ represents an integer of 2 to 80. ]

［式中、ｍ_２は５〜２０の整数を示す］

[Wherein m ₂ represents an integer of 5 to 20]

［式中、Ｑ^４及びＱ^９は各々独立に炭素数１〜５のアルキレン基又は置換基を有してもよいフェニレン基を示し、Ｑ^５、Ｑ^６、Ｑ^７、及びＱ^８は各々独立に炭素数１〜５のアルキル基、フェニル基又はフェノキシ基を示し、ｓは１〜５の整数を示す］

[Wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ are each independently Represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and s represents an integer of 1 to 5]

で表される脂肪族ジアミンの他、下記式（Ｘ）で表される脂肪族エーテルジアミンが挙げられる。 Specific examples of the aliphatic ether diamine represented by the general formula (IX) include the following formula:

In addition to the aliphatic diamine represented by the formula, an aliphatic ether diamine represented by the following formula (X) is exemplified.

（式中、ｐは０〜８０の整数を示す）

(Wherein p represents an integer of 0 to 80)

  Specific examples of the aliphatic diamine represented by the general formula (XI) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6. -Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diamino And cyclohexane.

  Specifically, as the siloxane diamine represented by the above general formula (XII), it is assumed that p in the formula (XII) is 1, 1,1,3,3-tetramethyl-1,3-bis (4 -Aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis (4-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (2 -Aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (2 -Aminoethyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (3 -Aminobutyl) disiloxane, 1,3-dimethyl 1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane and the like, and p is 2, and 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl 3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) tri Siloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy- 1,5-bis (4-aminobuty ) Trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1 , 5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5 , 5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane. These diamines can be used alone or in combination of two or more.

  Moreover, the said polyimide resin may mix (blend) 1 type individually or 2 types or more as needed.

  In addition, as described above, when determining the composition of the polyimide resin, it is preferable to design the Tg to be 140 ° C. or less. As the diamine that is the raw material of the polyimide resin, the general formula (X) It is preferable to use the aliphatic ether diamine represented. Specific examples of the aliphatic ether diamine represented by the above general formula (X) include Jeffamine D-230, D-400, D-2000, D-4000, ED-600, ED- manufactured by Sun Techno Chemical Co., Ltd. 900, ED-2000, EDR-148 (all trade names), BASF (manufactured by) polyetheramine D-230, D-400, D-2000 (all trade names) and other aliphatics such as polyoxyalkylene diamines Examples include diamines. These diamines are preferably 1 to 80 mol%, more preferably 5 to 60 mol% of the total diamine. If this amount is less than 1 mol%, it tends to be difficult to impart low-temperature adhesiveness and fluidity during heat. On the other hand, if it exceeds 80 mol%, the Tg of the polyimide resin becomes too low, Self-supporting tends to be impaired. By introducing such an aliphatic ether diamine into the polyimide resin, alkali solubility, organic solvent solubility, and compatibility with other components can be improved.

  The polyimide resin can be obtained by a reaction between a tetracarboxylic dianhydride and a diamine having a carboxyl group and an amino group, whereby a carboxyl group derived from the diamine is introduced into the polyimide. (A) When using a polyimide resin as an alkali-soluble resin, a polyimide resin having a Tg of 140 ° C. or lower and an Mw of 10,000 to 300,000 is particularly preferred by appropriately adjusting the type of diamine, its charging ratio, reaction conditions, and the like. .

  In the photosensitive adhesive composition of the present invention, the content of the component (A) is 5 to 90% by mass on the basis of the total solid content of the photosensitive adhesive composition from the viewpoint of pattern formation and adhesiveness. It is preferably 20 to 80% by mass. When this content is less than 5% by mass, the pattern formability tends to be impaired, and when it exceeds 90% by mass, the pattern formability and the adhesiveness tend to decrease.

<(B) component>
The (B) dihydropyridine derivative constituting the photosensitive adhesive composition of the present invention has a function as a photosensitive agent. From the viewpoint of reducing outgas and improving high-temperature adhesiveness, the dihydropyridine derivative (B) preferably has a 5% weight loss temperature of 150 ° C. or higher, and has an absorption band at 300 to 500 nm because the sensitivity is further improved. It is preferable. Here, the 5% weight loss temperature means that the sample was heated at a rate of 10 ° C./min with a nitrogen flow (400 mL / min) using a differential thermothermal gravimetric simultaneous measurement device (SII Nanotechnology, Inc .: TG / DTA6300). 5% weight loss temperature as measured under min).

  The (B) dihydropyridine derivative is not particularly limited, but for example, a compound represented by the following structural formula (V) is preferably used.

ここで、Ｒ^１は、水素原子、炭素数１〜１０のアルキル基、フェニル基、ベンジル基、ベンゾイル基、ナフチル基、水酸基又はニトロ基を示し、水素原子又は炭素数１〜１０のアルキル基であることが好ましく、水素原子であることがより好ましい。また、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に水素原子、炭素数１〜１０のアルキル基、フェニル基、ベンジル基、ベンゾイル基又はナフチル基を示す。Ｒ^２及びＲ^３は、炭素数１〜１０のアルキル基であることが好ましく、メチル基であることがより好ましい。Ｒ^４及びＲ^５は水素原子又は炭素数１〜１０のアルキル基であることが好ましく、水素原子又はメチル基であることがより好ましい。Ｒ^６は炭素数１〜１０のアルキル基であることが好ましく、メチル基又はエチル基であることがより好ましい。

Here, R ¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, a benzoyl group, a naphthyl group, a hydroxyl group or a nitro group, and is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. It is preferable that it is a hydrogen atom. R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, a benzyl group, a benzoyl group or a naphthyl group. R ² and R ³ are preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group. R ⁴ and R ⁵ are preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a methyl group. R ⁶ is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group or an ethyl group.

  When the adhesive film contains the (B) dihydropyridine derivative as described above, the adhesive property of the photosensitive resin composition to the adherend and the moisture resistance reliability can be improved. Outgassing can be reduced. These are considered to be due to the fact that the basicity of the dihydropyridine derivative is increased by light irradiation and promotes the reaction of the epoxy resin, and the volatile unreacted low molecular weight components can be reduced by the effect of promoting the reaction.

  When an alkali-soluble resin having a hydrophilic carboxyl group is used, there is a concern about a decrease in moisture resistance reliability such as an increase in water absorption and a decrease in adhesive strength after moisture absorption, but by blending (B) a dihydropyridine derivative, Since the reaction between the carboxyl group and the epoxy resin is promoted, the residual carboxyl group is reduced, and it is possible to have the effect of improving the moisture resistance reliability such as reducing the moisture absorption rate and maintaining the adhesive force after moisture absorption. .

  (B) The content of the dihydropyridine derivative is preferably 3 to 50 parts by mass, more preferably 5 to 40 parts by mass, and 10 to 30 parts by mass with respect to 100 parts by mass of the alkali-soluble resin. More preferably. (B) If the content of the dihydropyridine derivative is less than 3 parts by mass, the pattern formability tends to be reduced (reduction in film thickness after development). There is a tendency to decrease.

  You may add the compound which produces | generates a carboxyl group by light irradiation as needed to the photosensitive adhesive composition of this invention. Although it does not specifically limit as a compound which produces | generates a carboxyl group by the said light irradiation, A diazo naphthoquinone type photosensitive agent etc. are mentioned. By using in combination with these, it becomes possible to form a pattern with higher sensitivity and a lower photosensitizer concentration.

<(C) component>
As the (C) epoxy resin used in the present invention, those containing at least two epoxy groups in the molecule are preferable, and phenol glycidyl ether type epoxy resins are more preferable from the viewpoint of curability and cured product characteristics. Examples of such resins include bisphenol A type (or AD type, S type, and F type) glycidyl ether, water-added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, and propylene oxide adduct. Bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolac resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, dicyclo Examples include glycidyl ether of pentadienephenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. It is. These can be used alone or in combination of two or more.

  From the viewpoint of adhesiveness after curing, the (C) epoxy resin preferably contains a compound represented by the following structural formula (III).

  In addition, (C) the epoxy resin should be a high-purity product in which impurity ions such as alkali metal ions, alkaline earth metal ions, halogen ions, particularly chlorine ions and hydrolyzable chlorine are reduced to 300 ppm or less. It is preferable for preventing electromigration and preventing corrosion of metal conductor circuits.

  (C) It is preferable that it is 0.1-200 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, and, as for content of an epoxy resin, it is more preferable that it is 2-50 mass parts. When the content of the epoxy resin exceeds 200 parts by mass, the solubility in an alkaline aqueous solution tends to decrease and the pattern formability tends to decrease, and when it is less than 0.1 parts by mass, the high-temperature adhesiveness tends to decrease. There is.

<Other ingredients>
The photosensitive adhesive composition of the present invention can contain an epoxy resin curing agent, if necessary. The photosensitive adhesive composition further contains a curing agent, so that high adhesiveness and moisture resistance reliability are obtained at a relatively low temperature (120 to 180 ° C.), a short time (1 to 3 hours) and low outgas. It is done. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acids. Examples include dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines. Among these, phenol compounds are preferable, and phenol compounds having at least two phenolic hydroxyl groups in the molecule are more preferable. Examples of such compounds include phenol novolak, cresol novolak, t-butylphenol novolak, dicyclopentagen cresol novolak, dicyclopentagen phenol novolak, xylylene-modified phenol novolak, naphthol compound, trisphenol compound, tetrakisphenol. Examples include novolak, bisphenol A novolak, poly-p-vinylphenol, and phenol aralkyl resin. Among these, those having a number average molecular weight in the range of 400 to 1500 are preferable. Thereby, the outgas at the time of heating which causes the contamination of the semiconductor element or the device at the time of assembling the semiconductor device can be suppressed.

  From the viewpoints of adhesiveness after curing and alkali solubility, the compound having two or more phenolic hydroxyl groups in the molecule preferably includes a compound represented by the following structural formula (IV).

  Moreover, the photosensitive adhesive composition of this invention can also be made to contain a hardening accelerator as needed. The curing accelerator is not particularly limited as long as it cures an epoxy resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methyl. Examples include imidazole-tetraphenylborate and 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate. As for content of the hardening accelerator in a photosensitive adhesive composition, 0-50 mass parts is preferable with respect to 100 mass parts of epoxy resins.

  Moreover, the photosensitive adhesive composition of this invention can also contain thermosetting resins, such as polyfunctional (meth) acrylate, nadiimide, maleimide, as needed.

  Moreover, when adding the said polyfunctional (meth) acrylate, it is preferable to add the organic peroxide which produces | generates a radical seed | species by heating.

  Furthermore, a filler can also be used in the photosensitive adhesive composition of the present invention. Examples of the filler include metal fillers such as silver powder, gold powder, copper powder, and nickel powder, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, and magnesium oxide. Inorganic fillers such as aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide, and ceramics, and organic fillers such as carbon and rubber fillers. Regardless, it can be used without any particular restrictions.

  The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity, thermal conductivity, thixotropy, etc. to the photosensitive adhesive composition, and the non-metallic inorganic filler is added to the adhesive layer with thermal conductivity, low thermal expansion, low The organic filler is added for the purpose of imparting hygroscopicity, and the organic filler is added for the purpose of imparting toughness to the adhesive layer.

  These metal fillers, inorganic fillers, or organic fillers can be used singly or in combination of two or more. Among them, metal fillers, inorganic fillers or insulating fillers are preferable in terms of being able to impart conductivity, thermal conductivity, low moisture absorption characteristics, insulating properties, etc. required for adhesive materials for semiconductor devices, and inorganic fillers or insulating fillers. Among these, a silica filler is more preferable in that it has good dispersibility with respect to the resin varnish and can impart a high adhesive force when heated.

  The filler preferably has an average particle size of 10 μm or less and a maximum particle size of 30 μm or less, more preferably an average particle size of 5 μm or less and a maximum particle size of 20 μm or less. If the average particle diameter exceeds 10 μm and the maximum particle diameter exceeds 30 μm, the effect of improving fracture toughness tends to be difficult to obtain. Although there is no restriction | limiting in particular in a lower limit, Usually, both are 0.001 micrometer.

  The filler preferably satisfies both an average particle size of 10 μm or less and a maximum particle size of 30 μm or less. When a filler having a maximum particle size of 30 μm or less but an average particle size exceeding 10 μm is used, it tends to be difficult to obtain high adhesive strength. In addition, when a filler having an average particle size of 10 μm or less but a maximum particle size exceeding 25 μm is used, the particle size distribution tends to be widened and the adhesive strength tends to vary, and the photosensitive adhesive composition is thinned. When processed and used as a film, the surface becomes rough and the adhesive strength tends to decrease.

  Examples of the method for measuring the average particle size and the maximum particle size of the filler include a method of measuring the particle size of about 200 fillers using a scanning electron microscope (SEM). As a measuring method using SEM, for example, a sample obtained by adhering a semiconductor element and a semiconductor mounting support member using an adhesive layer and then heat-curing (preferably at 150 to 200 ° C. for 1 to 10 hours) is used. The method of producing, cutting the center part of this sample, and observing the cross section by SEM etc. is mentioned. At this time, it is preferable that the existence probability of the filler having a particle diameter of 30 μm or less is 80% or more of the total filler.

  Although content of the said filler is determined according to the characteristic or function to provide, 1-50 mass% is preferable with respect to the sum total of a resin component and a filler, 2-40 mass% is more preferable, 5-30 mass % Is more preferable. By increasing the amount of filler, a high elastic modulus can be achieved, and dicing performance (cutability by a dicer blade), wire bonding performance (ultrasonic efficiency), and adhesive strength during heating can be effectively improved. If the amount of the filler is increased more than necessary, the thermocompression bonding property tends to be impaired. Therefore, the filler content is preferably within the above range. The optimum filler content is determined in order to balance the required properties. Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

  In the photosensitive resin composition of the present invention, a sensitizer can be used as necessary in order to improve sensitivity. Examples of the sensitizer include camphorquinone, benzyl, diacetyl, benzyldimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl) ketal, 4,4′-dimethylbenzyl-dimethyl ketal, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, thio Sandton-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone, The compound containing an azide group is mentioned. These can be used alone or in combination of two or more.

  Various coupling agents can also be added to the photosensitive adhesive composition of the present invention in order to improve interfacial bonding between different materials. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based, and among them, a silane-based coupling agent is preferable because it is highly effective. It is preferable that the usage-amount of the said coupling agent shall be 0.01-20 mass parts with respect to the (A) alkali-soluble resin to be used and 100 mass parts from the surface of the effect, heat resistance, and cost.

  Furthermore, polymerization inhibitors such as quinones, polyhydric phenols, phenols, phosphites, sulfurs, etc. are used as polymerization inhibitors and antioxidants in order to impart storage stability, process adaptability, and antioxidant properties. And you may add antioxidant in the range which does not impair sclerosis | hardenability and heat resistance.

  In the photosensitive adhesive composition of the present invention, an ion scavenger can be further added in order to adsorb ionic impurities and improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, triazine thiol compound, a compound known as a copper damage preventer for preventing copper from being ionized and dissolved, such as a phenol-based reducing agent, Inorganic compounds such as bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, zuzu-based, and mixed systems thereof. Specific examples include inorganic ion scavengers manufactured by Toa Gosei Co., Ltd., trade names: IXE-300 (antimony type), IXE-500 (bismuth type), IXE-600 (antimony, bismuth mixed type), IXE-700. (Magnesium and aluminum mixed system), IXE-800 (zirconium system), IXE-1100 (calcium system) and the like. These can be used individually by 1 type or in mixture of 2 or more types. The amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin from the viewpoints of the effect of addition, heat resistance, cost, and the like.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a film adhesive according to the present invention. A film adhesive (adhesive film) 1 shown in FIG. 1 is obtained by forming the photosensitive adhesive composition into a film. FIG. 2 is a schematic cross-sectional view showing an embodiment of an adhesive sheet according to the present invention. The adhesive sheet 100 shown in FIG. 2 is comprised from the base material film (base material) 3 and the adhesive bond layer which consists of the adhesive film 1 provided on this one surface. FIG. 3 is a schematic cross-sectional view showing another embodiment of the adhesive sheet according to the present invention. The adhesive sheet 110 shown in FIG. 3 is comprised from the base material 3, the film adhesive 1 and the cover film 2 which were provided on these one surfaces.

  The film adhesive 1 is prepared by mixing (A) an alkali-soluble resin, (B) a dihydropyridine derivative, and (C) an epoxy resin, and other components added as necessary in an organic solvent. A varnish is prepared by kneading, a layer of this varnish is formed on the substrate 3, and the substrate 3 is removed after drying the varnish layer by heating. At this time, the substrate 3 can be stored and used in the state of the adhesive sheets 100 and 110 without removing the substrate 3.

  The above mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. In addition, it dries on the conditions which thermosetting resin, such as (C) epoxy resin, does not fully react during drying, and the solvent volatilizes sufficiently. Specifically, the varnish layer is dried by heating at 60 to 180 ° C. for 0.1 to 90 minutes. The preferred thickness of the varnish layer before drying is 1 to 100 μm. If this thickness is less than 1 μm, the adhesive fixing function tends to be impaired, and if it exceeds 100 μm, the residual volatile matter described later tends to increase.

  The preferred residual volatile content of the obtained varnish layer is 10% by mass or less. If this residual volatile content exceeds 10% by mass, voids tend to remain inside the adhesive layer due to foaming due to solvent volatilization during assembly heating, and the moisture resistance reliability tends to be impaired. There is also a tendency that the possibility of contamination of surrounding materials or members due to the generated volatile components increases. In addition, the measurement conditions of said residual volatile component are as follows. That is, for a film-like adhesive cut to a size of 50 mm × 50 mm, the initial mass is M1, and the mass after heating this film-like adhesive in an oven at 160 ° C. for 3 hours is M2, [(M1-M2 ) / M1] × 100 = value when residual volatile content (%).

  The temperature at which the thermosetting resin does not sufficiently react is specifically determined by using DSC (for example, “DSC-7 type” (trade name) manufactured by PerkinElmer Co., Ltd.) It is the temperature below the peak temperature of the reaction heat when measured under the conditions of 10 mg, temperature increase rate: 5 ° C./min, measurement atmosphere: nitrogen.

  The organic solvent used for preparing the varnish, that is, the varnish solvent is not particularly limited as long as the material can be uniformly dissolved or dispersed. Examples include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidinone.

  The 5% weight reduction temperature of the film adhesive 1 formed using the varnish is preferably 180 ° C. or higher, more preferably 220 ° C. or higher, and particularly preferably 260 ° C. or higher. When the 5% weight reduction temperature is 180 ° C. or more, outgassing due to the heat history after curing is reduced, and contamination of the semiconductor element and peeling of the adherend can be suppressed.

The film-like adhesive 1 has a flow amount of 200 μm or more, preferably 200 to 5000 μm, preferably 200 to 3000 μm when pressed at 0.2 MPa for 60 seconds while being heated to 180 ° C. More preferred. Satisfying this condition can ensure good thermocompression bonding at low temperatures. Here, the flow amount is measured on a test piece cut out to a size of 10 mm × 10 mm from the adhesive layer prepared to have a thickness of 50 μm ± 5 μm. That is, the test piece was sandwiched between two slide glasses (manufactured by MATUNAMI, 76 mm × 26 mm × 1.0 to 1.2 mm thickness), and the whole was heated on a hot plate at 180 ° C. while being 2 kgf / cm ^2. The average value of the amount of protrusion of the adhesive layer from the four sides of the PET base material after heating and pressurizing for 60 seconds by applying a load of (0.2 MPa) is defined as the flow amount. The protruding amount of the adhesive layer means the distance from the extreme end portion of the protruding adhesive layer to the PET substrate and can be measured by observation using an optical microscope.

  When the flow amount is less than 200 μm, it tends to be difficult to fill the uneven surface of the support member due to heat and pressure, and bubbles tend to remain on the uneven surface of the support member. It becomes a starting point and becomes easy to foam during reflow. On the other hand, when the flow amount exceeds 5000 μm, it tends to be impossible to maintain the pattern shape.

  The photosensitive adhesive composition of the present invention can form either a positive image or a negative image depending on the blending ratio and blending components, but it is a flow during heat after pattern formation, which is one of the objects of the present invention. From the viewpoint of safety, a positive image is more preferable.

  The substrate 3 is not particularly limited as long as it can withstand the above drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, or a methylpentene film can be used as the substrate 3. The film as the substrate 3 may be a multilayer film in which two or more kinds are combined, or the surface may be treated with a release agent such as a silicone or silica.

  Moreover, the film adhesive 1 of this invention and a dicing sheet can be laminated | stacked, and it can also be set as an adhesive sheet. The dicing sheet is a sheet provided with a pressure-sensitive adhesive layer on a substrate, and the pressure-sensitive adhesive layer may be either a pressure-sensitive type or a radiation curable type. The base material is preferably an expandable base material. By using such an adhesive sheet, a dicing / die bonding integrated adhesive sheet having both a function as a die bond film and a function as a dicing sheet can be obtained.

  Specifically, as the dicing / die bonding integrated adhesive sheet, as shown in FIG. 4, there is an adhesive sheet 120 in which the base film 7, the pressure-sensitive adhesive layer 6, and the film adhesive 1 of the present invention are formed in this order. Can be mentioned.

  FIG. 5 is a top view showing an embodiment of a semiconductor wafer with an adhesive layer according to the present invention, and FIG. 6 is an end view taken along line IV-IV in FIG. A semiconductor wafer 20 with an adhesive layer shown in FIGS. 5 and 6 includes a semiconductor wafer 8 and a film adhesive (adhesive layer) 1 made of the photosensitive adhesive composition provided on one surface of the semiconductor wafer 8. Prepare.

  The semiconductor wafer 20 with an adhesive layer is obtained by laminating the film adhesive 1 on the semiconductor wafer 8 while heating. Since the film adhesive 1 is a film made of the photosensitive adhesive composition, it can be attached to the semiconductor wafer 8 at a low temperature of about room temperature (25 ° C.) to 150 ° C., for example.

  7 and 9 are top views showing an embodiment of the adhesive pattern according to the present invention, FIG. 8 is an end view taken along the line V-V in FIG. 7, and FIG. It is an end view along line -VI. The adhesive patterns 1a and 1b shown in FIGS. 7, 8, 9 and 10 are formed on the semiconductor wafer 8 as the adherend so as to have a pattern along a substantially square side or a square pattern.

  The adhesive patterns 1a and 1b are obtained by forming an adhesive layer 1 made of a photosensitive adhesive composition on a semiconductor wafer 8 as an adherend to obtain a semiconductor wafer 20 with an adhesive layer. It is formed by exposing through a mask and developing the exposed adhesive layer 1 with an alkaline developer. Thereby, semiconductor wafers 20a and 20b with an adhesive layer in which adhesive patterns 1a and 1b are formed are obtained.

  As a use of the film adhesive of the present invention, a semiconductor device provided with a film adhesive will be specifically described with reference to the drawings. In recent years, semiconductor devices having various structures have been proposed, and the use of the film adhesive of the present invention is not limited to the semiconductor devices having the structure described below.

  FIG. 11 is a schematic cross-sectional view showing an embodiment of a semiconductor device of the present invention. In the semiconductor device 200 shown in FIG. 11, the semiconductor element 12 is bonded to the semiconductor element mounting support member 13 via the film adhesive 1 of the present invention, and the connection terminal (not shown) of the semiconductor element 12 has the wire 14. And is electrically connected to an external connection terminal (not shown) via a sealing material 15.

  FIG. 12 is a schematic cross-sectional view showing another embodiment of the semiconductor device of the present invention. In the semiconductor device 210 shown in FIG. 12, the first-stage semiconductor element 12a is bonded to the semiconductor-element mounting support member 13 on which the terminals 16 are formed via the film adhesive 1 of the present invention. A second-stage semiconductor element 12b is further bonded onto 12a via the film adhesive 1 of the present invention. The connection terminals (not shown) of the first-stage semiconductor element 12a and the second-stage semiconductor element 12b are electrically connected to the external connection terminals via the wires 14, and are sealed with a sealing material. Thus, the film adhesive of the present invention can be suitably used for a semiconductor device having a structure in which a plurality of semiconductor elements are stacked.

  The semiconductor device (semiconductor package) shown in FIGS. 11 and 12 is, for example, a semiconductor wafer 20b shown in FIG. 9 is diced along a broken line D, and the semiconductor element with a film adhesive after dicing is used as a semiconductor element mounting support member. It can be obtained by thermocompression bonding to 13 and bonding them together, followed by a wire bonding step and, if necessary, a step such as a sealing step with a sealing material. The heating temperature in the thermocompression bonding is usually 20 to 250 ° C., the load is usually 0.01 to 20 kgf, and the heating time is usually 0.1 to 300 seconds.

  As mentioned above, although preferred embodiment of this invention was described, this invention is not restrict | limited to this.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

(Measurement of molecular weight)
The weight average molecular weight (Mw) of the polyimide resin was measured by high performance liquid chromatography (C-R4A) manufactured by Shimadzu Corporation and calculated by a calibration curve using standard polystyrene. The measurement conditions for GPC are shown below.
Column: Gelpack GL-S300MDT-5 × 2
Eluent: DMF + LiBr (0.06 mol / L) + phosphoric acid (0.06 mol / L)
Flow rate: 1.0 mL / min

(Measurement of glass transition temperature)
The glass transition temperature (Tg) of the polyimide resin is a main dispersion peak temperature when the polyimide resin is formed into a film, measured under the following conditions, and the tan δ peak temperature is defined as the main dispersion temperature.
Apparatus: Viscoelasticity analyzer “RSA-2” (manufactured by Rheometrics)
Temperature rising rate: 5 ° C / min Frequency: 1Hz
Measurement temperature: -150 to 300 ° C

(Synthesis of polyimide PI-1)
In a flask equipped with a stirrer, a thermometer, a condenser tube and a nitrogen substitution device, 1.89 g of 3,5-diaminobenzoic acid (molecular weight 152.2, hereinafter referred to as “DABA”), aliphatic ether diamine (manufactured by BASF, Trade name “D-400”, molecular weight 452.4) 15.21 g, 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “ LP-7100 ", molecular weight 248.5) 0.39 g and N-methyl-2-pyrrolidinone (hereinafter" NMP ") 116 g were charged.

  Next, 16.88 g of 4,4′-oxydiphthalic dianhydride (molecular weight 326.3, hereinafter referred to as “ODPA”) was added in small portions into the flask while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

  Next, a reflux condenser with a moisture receiver was attached to the flask, 70 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 5 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature and then poured into distilled water for reprecipitation. Then, the obtained deposit was dried with the vacuum dryer and polyimide resin (henceforth "polyimide PI-1") was obtained. Mw of polyimide PI-1 was 33000, and Tg was 55 ° C.

(Synthesis of polyimide PI-2)
In a flask equipped with a stirrer, a thermometer, and a nitrogen substitution device, 2.16 g of 5,5′-methylene-bis (anthranic acid) (molecular weight 286.3, hereinafter referred to as “MBAA”), “D-400” 15.13 g, “LP7100” 1.63 g and NMP 115 g were charged.

  Next, 16.51 g of ODPA was added in small portions into the flask while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

  Next, a reflux condenser with a moisture receiver was attached to the flask, 81 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 5 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature, and then poured into distilled water for reprecipitation to obtain a polyimide (hereinafter referred to as “polyimide PI-2”). Mw of polyimide PI-2 was 30000, and Tg was 31 ° C.

(Synthesis of polyimide PI-3)
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 11.44 g of MBAA, 17.32 g of “D-400”, 2.49 g of “LP7100” and 100 g of NMP were charged.

  Next, 31 g of ODPA was added in small portions into the flask while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

  Next, a reflux condenser with a moisture receiver was attached to the flask, 81 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 5 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature, and then poured into distilled water for reprecipitation to obtain a polyimide (hereinafter referred to as “polyimide PI-3”). Mw of polyimide PI-3 was 38000, and Tg was 65 ° C.

(Synthesis of polyimide PI-4)
In a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device, 17.16 g of MBAA, 8.66 g of “D-400”, 2.49 g of “LP7100” and 100 g of NMP were charged.

  Next, 31 g of ODPA was added in small portions into the flask while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

  Next, a reflux condenser with a moisture receiver was attached to the flask, 81 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 5 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature, and then poured into distilled water for reprecipitation to obtain a polyimide (hereinafter referred to as “polyimide PI-4”). Mw of polyimide PI-4 was 44000, and Tg was 150 ° C.

(Synthesis of polyimide PI-5)
MBAA (13.9 g) and NMP (115 g) were charged into a flask equipped with a stirrer, a thermometer, and a nitrogen displacement device.

  Next, 16.51 g of ODPA was added in small portions into the flask while the flask was cooled in an ice bath. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

  Next, a reflux condenser with a moisture receiver was attached to the flask, 81 g of xylene was added, the temperature was raised to 180 ° C. while blowing nitrogen gas, the temperature was maintained for 3 hours, and xylene was removed azeotropically with water. . The solution thus obtained was cooled to room temperature, and then poured into distilled water for reprecipitation to obtain a polyimide (hereinafter referred to as “polyimide PI-5”). Mw of polyimide PI-5 was 42000, and Tg was 185 ° C.

(Examples 1-3 and Comparative Examples 1-4)
Each of the above PI-1 to 5 was used, and each component was blended at a composition ratio (unit: part by mass) shown in Table 1 to prepare a photosensitive resin composition (varnish for forming an adhesive layer).

In addition, the symbol of each component in Table 1 means the following.
VG-3101: Trifunctional epoxy resin manufactured by Printec,
EXA-4850-150: manufactured by Dainippon Ink & Chemicals, Inc., bifunctional epoxy resin,
TrisP-PA: manufactured by Honshu Chemical Industry Co., Ltd., trisphenol compound (α, α, α′-tris (4-hydroxyphenol) -1-ethyl-4-isopropylbenzene),
R972: manufactured by Nippon Aerosil Co., Ltd., hydrophobic fumed silica (average particle size: about 16 nm),
Nifedivin (dihydropyridine derivative): 2,4-dihydro-2,6-dimethyl-4- (2-nitrophenyl) -3,5-pyridinedicarboxylic acid dimethyl ester manufactured by Tokyo Chemical Industry Co., Ltd.

  The obtained varnish for forming an adhesive layer was applied onto a substrate (peeling agent-treated PET film) so that the film thickness after drying was 40 μm, and then in an oven at 80 ° C. for 30 minutes, The adhesive sheet of Examples 1-3 and Comparative Examples 1-4 with which the adhesive bond layer was formed on the base material was heated for 10 minutes at 120 degreeC.

<Evaluation of low temperature adhesiveness>
The adhesive sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 4 were rolled on a silicon wafer (6 inch diameter, thickness 400 μm) placed on a support base with the adhesive layer facing the silicon wafer (temperature). The layers were laminated by pressurizing at 100 ° C., linear pressure of 4 kgf / cm, and feeding speed of 0.5 m / min. Next, the base material (PET film) is peeled off, and a polyimide film having a thickness of 80 μm, a width of 10 mm, and a length of 40 mm is placed on the adhesive layer by a roll under the same conditions as above (trade name “UPILEX”). Pressurized and laminated.

  The sample thus prepared was subjected to a 90 ° peel test at room temperature using a rheometer (trade name “Strograph ES” manufactured by Toyo Seisakusho Co., Ltd.), and the peel between the adhesive layer and the upilex was measured. The strength was measured. Based on the measurement results, a sample having a peel strength of 2 N / cm or more was evaluated as A, and a sample having a peel strength of less than 2 N / cm was evaluated as B. The results are shown in Table 2.

<Evaluation of pattern formability>
The adhesive sheet is pressed on a silicon wafer (6 inch diameter, thickness 400 μm) at a temperature of 100 ° C. with a roll with the adhesive layer facing the silicon wafer (linear pressure 4 kgf / cm, feed rate 0.5 m / min) It laminated | stacked by doing. Next, a mask for pattern (manufactured by Hitachi Chemical Co., Ltd., trade name: “No. G-2”) is placed on the substrate (PET film), and a high precision parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name: “EXM”). −1172-B-∞ ”) at 500 mJ / cm ² .

  Thereafter, the base material (PET film) was removed, and using a conveyor developing machine (manufactured by Yako Co., Ltd.), a 2.38 mass% solution of tetramethylammonium hydride (TMAH) was used as the developer, temperature 27 ° C., spray pressure 0.18 MPa. After spray development under the conditions, the film was washed with pure water at a temperature of 23 ° C. under a spray pressure of 0.02 MPa. After development, whether or not a pattern of line width / space width = 400 μm / 400 μm was formed was visually confirmed, and the case where the pattern was formed was evaluated as A, and the case where the pattern was not formed was evaluated as B. The results are shown in Table 2.

<Evaluation of thermocompression bonding (flow amount) after pattern formation>
A test piece cut out to a size of 10 mm × 10 mm from an adhesive layer prepared to have a thickness of 50 μm is placed between two slide glasses (manufactured by MATSANAMI, 76 mm × 26 mm × 1.0 to 1.2 mm thick). After heating and pressurizing for 60 seconds by applying a load of ² kgf / cm ² (0.2 MPa) while heating the whole on a hot plate at 180 ° C., adhesion from the four sides of the PET base material The average amount of protrusion of the agent layer was taken as the flow amount. The protruding amount of the adhesive layer means the distance from the extreme end of the protruding adhesive layer to the PET substrate, and was measured by observation using an optical microscope. The results are shown in Table 2.

<Measurement of 260 ° C. Peel Strength (Evaluation of Adhesiveness at High Temperature (Heat Resistance after Adhesion))>
A silicon wafer (6 inch diameter, 400 μm thick) was half cut to a size of 5 mm × 5 mm to a depth of 180 μm. Then, the adhesive sheet of Examples 1 and 2 and Comparative Examples 1 and 3 is 60 ° C., the adhesive sheet of Comparative Example 2 is 250 ° C., and the adhesive layer is formed on a half-cut silicon wafer. Lamination was performed on the silicon wafer side by pressing with a roll (linear pressure 4 kgf / cm, feed rate 0.5 m / min). And the obtained sample was exposed at 500 mJ / cm < ² > with the high precision parallel exposure machine (The Oak Manufacturing Co., Ltd. make, brand name: "EXM-1172-B-infinity").

  Thereafter, the base material (PET film) was removed, and the sample was separated into 5 mm × 5 mm pieces. The separated silicon wafer with the adhesive layer is placed on a glass substrate (10 mm × 10 mm × thickness 0.55 mm) with the adhesive layer facing the glass substrate side, and pressurized at 2 kgf for 10 seconds at 120 ° C. Crimped. The test piece thus obtained was cured by heating in an oven at 180 ° C. for 1 hour. Thereafter, the test piece was heated on a heating plate at 260 ° C. for 10 seconds, and the peel strength of the silicon wafer at 260 ° C. was measured at a measurement speed of 0.5 mm / sec using the peel strength measuring apparatus shown in FIG. The value at this time was defined as 260 ° C. peel strength. The results are shown in Table 2.

  In the peel strength measuring device 300 shown in FIG. 13, a handle 32 is provided around the fulcrum 33 at a variable angle at the tip of a rod attached to the push-pull gauge 31. The 260 ° C. peel strength is measured by placing a test piece on which a silicon wafer 34 having a protrusion and a glass substrate 35 are bonded via an adhesive layer 1 on a heating plate 36 at 260 ° C. The peel stress when the handle 32 was moved at 0.5 mm / second in a state where the handle 32 was hooked on the protruding portion 34 was measured by the push-pull gauge 31.

  As is clear from the results in Table 2, the adhesive sheets obtained in Examples 1 to 3 are superior in low-temperature sticking property and pattern formability compared to the adhesive sheets obtained in Comparative Examples 1 to 4, and heat It was confirmed that the time fluidity and 260 ° peel strength were sufficiently high.

It is a schematic cross section which shows one Embodiment of the film adhesive which concerns on this invention. It is a schematic cross section which shows one Embodiment of the adhesive sheet which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet which concerns on this invention. It is a schematic cross section which shows other one Embodiment of the adhesive sheet which concerns on this invention. It is a top view which shows one Embodiment of the semiconductor wafer with an adhesive layer which concerns on this invention. FIG. 6 is an end view taken along line IV-IV in FIG. 5. It is a top view which shows one Embodiment of the adhesive agent pattern which concerns on this invention. FIG. 8 is an end view taken along line VV in FIG. 7. It is a top view which shows one Embodiment of the adhesive agent pattern which concerns on this invention. FIG. 10 is an end view taken along line VI-VI in FIG. 9. It is a schematic cross section showing one embodiment of a semiconductor device of the present invention. It is a schematic cross section which shows other one Embodiment of the semiconductor device of this invention. It is the schematic which shows a peel strength measuring apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Film adhesive (adhesive layer), 1a, 1b ... Adhesive pattern, 2 ... Cover film, 3 ... Base film (base material), 6 ... Adhesive layer, 7 ... Base film, 8 ... Semiconductor Wafer, 12, 12a, 12b ... semiconductor element, 13 ... semiconductor element mounting support member, 14 ... wire, 15 ... sealing material, 16 ... terminal, 20, 20a, 20b ... semiconductor wafer with adhesive layer, 31 ... push Pull gauge, 32 ... handle, 33 ... fulcrum, 34 ... silicon wafer, 35 ... glass substrate, 100, 110, 120 ... adhesive sheet, 200, 210 ... semiconductor device, 300 ... peel strength measuring device.

Claims (14)

A photosensitive adhesive composition containing (A) an alkali-soluble resin, (B) a dihydropyridine derivative and (C) an epoxy resin,
The (A) alkali-soluble resin is a polyimide resin obtained by reacting tetracarboxylic dianhydride and diamine,
The diamine includes a diamine having a carboxyl group and / or a hydroxyl group in the molecule, and an aliphatic ether diamine represented by the following formula (X):
The (B) dihydropyridine derivative is nifedivine,
The (C) epoxy resin is a phenol glycidyl ether type epoxy resin ,
The photosensitive resin composition whose glass transition temperature of said (A) alkali-soluble resin is -20-140 degreeC.

(Wherein p represents an integer of 0 to 80) 2. The photosensitive adhesive composition according to claim 1, wherein the flow amount is 200 μm or more when formed into a film and then pressed at 0.2 MPa for 60 seconds while being heated to 180 ° C. 3. The photosensitive adhesive composition of Claim 1 or 2 whose content of the aliphatic ether diamine represented by the said formula (X) is 1-80 mol% of all the diamines. Diamines having a carboxyl group and / or hydroxyl group in the molecule, an aromatic diamine represented by the following structural formulas aromatic diamine and / or the following structural formula represented by (I) (II), according to claim 1 The photosensitive adhesive composition as described in any one of -3.

The photosensitive adhesive according to claim 4, wherein the aromatic diamine represented by the structural formula (I) and the aromatic diamine represented by the structural formula (II) are 1 to 50 mol% of the total diamine. Composition. (D) The photosensitive adhesive composition as described in any one of Claims 1-5 which further contains the compound which has a 2 or more phenolic hydroxyl group in a molecule | numerator. The photosensitive adhesive composition according to claim 6 , wherein the compound (D) having two or more phenolic hydroxyl groups in the molecule includes a compound represented by the following structural formula (IV).

The (C) epoxy resin comprises a compound represented by the following structural formula (III), a photosensitive adhesive composition according to any one of claims 1-7.

The film adhesive which forms the photosensitive adhesive composition as described in any one of Claims 1-8 in a film form. Comprising a substrate and, an adhesive layer comprising a photosensitive adhesive composition according to any one of claims 1 to 8 provided on one surface of the substrate, the adhesive sheet. An adhesive layer made of the photosensitive adhesive composition according to any one of claims 1 to 8 is formed on an adherend, the adhesive layer is exposed through a photomask, and after the exposure An adhesive pattern formed by developing the adhesive layer with an alkaline aqueous solution. And the semiconductor wafer, and an adhesive layer comprising a photosensitive adhesive composition according to any one of claims 1 to 8 provided on one surface of the semiconductor wafer, the semiconductor wafer with an adhesive layer . Using the photosensitive adhesive composition according to any one of claims 1-8, the support member is formed by bonding the semiconductor element and the semiconductor element mounting, the semiconductor device. The manufacturing method of a semiconductor device which has the process of adhere | attaching a semiconductor element and the supporting member for semiconductor element mounting using the photosensitive adhesive composition as described in any one of Claims 1-8 .

Images