JP2015072409A - Photosensitive adhesive composition, method of producing semiconductor device using the same, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive adhesive composition enabling consecutive pressure-bonding in production of a semiconductor device by lamination of a plurality of semiconductor chips, keeping excellent performance when left on a stage, and having buffer coat characteristics allowing the formation of a thin and high-definition adhesive pattern.SOLUTION: A photosensitive adhesive composition comprises (A) an alkali soluble copolymer resin having a structural unit represented by a specific formula, (B) a compound that generates acid by light, (C) a heat crosslinking agent, and (D) an acrylic resin having a structural unit represented by another specific formula.

Description

  The present invention relates to a positive photosensitive adhesive composition used for an adhesive layer when stacking semiconductor devices, a method for manufacturing a semiconductor device using the same, and a semiconductor device.

  In recent years, a semiconductor device having a multilayer structure in which a plurality of semiconductor chips are stacked has attracted attention. In the manufacture of a semiconductor device, a die attach film for adhering semiconductor chips is required to stack the semiconductor chips. In recent years, however, there has been an increasing demand for reducing the thickness of semiconductor devices, and there is a need to reduce the thickness of the semiconductor chip itself. However, reducing the thickness of the chip itself is approaching its limit.

  Therefore, for the purpose of reducing the thickness of the die attach film, as described in Patent Document 1 and Patent Document 2, the buffer coat layer formed on the surface of the semiconductor chip is provided with an adhesive function, and the die attach film. The manufacturing method which makes it less is proposed. In this method, the curing temperature of the photosensitive adhesive composition is required to have a low temperature curing characteristic at about 170 to 180 ° C. in order to avoid deterioration of characteristics due to heat of the semiconductor chip.

JP 2012-186295 A Japanese Patent No. 5077023 Japanese Patent No. 5067028

  When the positive photosensitive adhesive composition is used as a buffer coat / adhesive layer for the above production method, the photosensitive resin film needs to have a certain degree of flexibility during the bonding process. However, when the conventional photosensitive resin composition for use in a surface protective film capable of being cured at a low temperature shown in Patent Document 3 is used, the reaction of the cross-linking agent gradually occurs when left on a pressure-bonding stage for a long time when performing continuous pressure-bonding. However, the adhesiveness gradually deteriorated.

  In order to solve the above-mentioned problems, the present inventors diligently investigated the adhesiveness at the time of continuous pressure bonding, which has not been studied in the conventional photosensitive resin composition for buffer coat. As a result, by using a base resin having a flexible skeleton, a photosensitive resin having the same photosensitive characteristics and cured film physical properties as those of the buffer coating photosensitive resin composition, and having a continuous pressure bonding property and excellent in stage leaving property. The present inventors have found an adhesive composition and completed the present invention.

  The photosensitive adhesive composition according to the present invention comprises (A) an alkali-soluble resin having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2); A compound that generates an acid by light, (C) a thermal crosslinking agent, (D) an acrylic resin having a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4); Containing.

［一般式（１）中、Ｒは水素原子又はメチル基を示し、Ｒ^１は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜１０のアルコキシ基を示し、ａは０〜３、ｂは１〜３の整数を示す。一般式（２）中、Ｒは水素原子又はメチル基を示し、Ｒ^２は１価の有機基を示す。］

[In General Formula (1), R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, a represents an integer of 0 to 3, and b represents an integer of 1 to 3. In the general formula (2), R represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group. ]

［一般式（３）中、Ｒは水素原子又はメチル基を示し、Ｒ^３は炭素数４〜２０のアルキル基を示す。一般式（４）中、Ｒは水素原子又はメチル基を示し、Ｒ^４は炭素数２〜２０のヒドロキシアルキル基を示す。］

[In General Formula (3), R represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 4 to 20 carbon atoms. In the general formula (4), R represents a hydrogen atom or a methyl group, and R ⁴ represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]

  From the viewpoint of giving higher sensitivity, it is preferable that the component (D) further has a structural unit represented by the following general formula (5).

［一般式（５）中、Ｒは水素原子又はメチル基を示す。］

[In General Formula (5), R represents a hydrogen atom or a methyl group. ]

  From the viewpoint of improving the compatibility between the component (D) and the component (A), and from the viewpoint of further improving the adhesion, mechanical properties and thermal shock resistance of the obtained pattern cured film to the substrate, the component (D) Preferably further has a structural unit represented by the following general formula (6).

［一般式（６）中、Ｒは水素原子又はメチル基を示し、Ｒ^５は１級、２級又は３級アミノ基を有する１価の有機基を示す。］

[In General Formula (6), R represents a hydrogen atom or a methyl group, and R ⁵ represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]

  Since the sensitivity at the time of forming a cured pattern film is further improved, the component (B) is preferably an o-quinonediazide compound.

  The cured film obtained by heat curing the photosensitive adhesive composition of the present invention at a low temperature has a high elongation at break and a low elastic modulus. In addition, it has excellent adhesiveness against leaving the stage during the bonding process.

  The present invention also includes a step of applying the photosensitive adhesive composition of the present invention to a circuit surface of a semiconductor wafer and drying to form a photosensitive adhesive composition film, and a predetermined step of the photosensitive adhesive composition film. A step of exposing a portion; a step of developing the photosensitive adhesive composition film after the exposure to remove the predetermined portion; and a step of heating the semiconductor wafer on which the pattern is formed A step of removing the residual solvent, a step of performing an ashing process after removing the insulating film of the predetermined portion of the photosensitive adhesive composition film by etching, and a step of thinning the wafer and separating the chips. The manufacturing method of a semiconductor device provided with the process of laminating | stacking a chip | tip, and the process of heat-hardening an adhesive bond layer is provided. According to this manufacturing method, a plurality of semiconductor chips can be continuously mounted, and the semiconductor device can be manufactured efficiently.

  According to the present invention, a photosensitive adhesive composition having excellent buffer coat properties and excellent adhesion to standing on the stage during the bonding process, and a method of manufacturing a semiconductor device using the same, photosensitive A semiconductor device having a conductive adhesive layer can be provided. Moreover, the pattern cured film which consists of the photosensitive adhesive composition which has the buffer coat characteristic of this invention shows the outstanding crack resistance and adhesiveness, and has a favorable photosensitive characteristic (sensitivity and resolution). In addition, since the photosensitive adhesive composition having the buffer coating characteristics of the present invention can be cured at a low temperature, the semiconductor device can be prevented from being damaged by heat, and a highly reliable semiconductor device can be obtained with a high yield. Can be provided.

It is sectional drawing which shows an example of the semiconductor chip produced using the photosensitive adhesive composition of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the present specification, “(meth) acrylate” means “acrylate” and “methacrylate” corresponding thereto. Similarly, “(meth) acryl” means “acryl” and “methacryl” corresponding thereto.

[Photosensitive adhesive composition having buffer coat properties]
The photosensitive adhesive composition having buffer coat properties according to the present embodiment includes (A) an alkali-soluble component having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). A copolymer resin, (B) a compound that generates an acid by light, (C) a thermal crosslinking agent, (D) a structural unit represented by the following general formula (3), and a general formula (4) And an acrylic resin having a structural unit.

［一般式（１）中、Ｒは水素原子又はメチル基を示し、Ｒ^１は炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基又は炭素数１〜１０のアルコキシ基を示し、ａは０〜３、ｂは１〜３の整数を示す。一般式（２）中、Ｒは水素原子又はメチル基を示し、Ｒ^２は１価の有機基を示す。］

[In General Formula (1), R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, a represents an integer of 0 to 3, and b represents an integer of 1 to 3. In the general formula (2), R represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group. ]

［一般式（３）中、Ｒは水素原子又はメチル基を示し、Ｒ^３は炭素数４〜２０のアルキル基を示す。一般式（４）中、Ｒは水素原子又はメチル基を示し、Ｒ^４は炭素数２〜２０のヒドロキシアルキル基を示す。］

[In General Formula (3), R represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 4 to 20 carbon atoms. In the general formula (4), R represents a hydrogen atom or a methyl group, and R ⁴ represents a hydroxyalkyl group having 2 to 20 carbon atoms. ]

<(A) component: alkali-soluble resin>
The component (A) is an alkali-soluble copolymer resin having a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).

In general formula (1), R represents a hydrogen atom or a methyl group. In the above formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group. These may be linear or branched. Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoints of heat resistance and alkali developability. Moreover, as a C6-C10 aryl group, a phenyl group, a naphthyl group, etc. are mentioned, As a C1-C10 alkoxy group, the alkyl part which the alkyl part mentioned as said C1-C10 alkyl group is mentioned. What is a group is mentioned, Specifically, a methoxy group, an ethoxy group, etc. are mentioned.

  In general formula (1), a represents an integer of 0 to 3, and b represents an integer of 1 to 3. a is preferably from 0 to 1, and b is preferably from 1 to 2.

In general formula (2), R represents a hydrogen atom or a methyl group. In the general formula (2), R ² represents a monovalent organic group. Specific examples of R ² include an organic group having 1 to 10 carbon atoms. Examples of such an organic group include an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group, and an alkoxyalkyl group. Can be mentioned. In these organic groups, the alkyl part of the alkyl group and the alkoxyalkyl group may be linear, branched or cyclic. R ² may be an organic group including a cyclic ether structure or a ring structure such as an aromatic ring. Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoints of heat resistance and alkali developability.

  The component (A) includes a monomer represented by the following general formula (7) that gives a structural unit represented by the general formula (1) when polymerized, and a structure represented by the general formula (2) when polymerized. It may be a copolymer with a monomer represented by the following general formula (8) which gives a unit. In addition, in one (A) component, a plurality of different structural units represented by the general formula (1) may exist, and the same can be said for the structural unit represented by the general formula (2). .

［一般式（７）におけるＲ、Ｒ^１、ａ、ｂは、それぞれ一般式（１）におけるＲ、Ｒ^１、ａ、ｂと同じ意味であり、一般式（８）におけるＲ、Ｒ^２は、それぞれ一般式（２）におけるＲ、Ｒ^２と同じ意味である。］

[R, R ¹ , a, and b in General Formula (7) have the same meanings as R, R ¹ , a, and b in General Formula (1), respectively, and R and R ² in General Formula (8) are Each has the same meaning as R and R ² in formula (2). ]

  Examples of the monomer represented by the general formula (7) include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, o-isopropenylphenol and the like. These monomers can be used alone or in combination of two or more. Among these, p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene are preferable from the viewpoints of cured film properties and alkali developability.

  Monomers represented by the general formula (8) include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid. Pentyl ester, (meth) acrylic acid hexyl ester, (meth) acrylic acid heptyl ester, (meth) acrylic acid octyl ester, (meth) acrylic acid nonyl ester, (meth) acrylic acid decyl ester, (meth) acrylic acid hydroxymethyl Ester, (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid hydroxybutyl ester, (meth) acrylic acid hydroxypentyl ester, (meth) acrylic acid hydroxyhexyl ester, (meth) Crylic acid hydroxyheptyl ester, (meth) acrylic acid hydroxyoctyl ester, (meth) acrylic acid hydroxynonyl ester, (meth) acrylic acid hydroxydecyl ester, (meth) acrylic acid butoxyethyl ester, (meth) acrylic acid butoxydiethylene glycol ester , (Meth) acrylic acid methoxytriethylene glycol ester, (meth) acrylic acid cyclohexyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid phenoxyethyl ester, (meth) Examples thereof include isobornyl acrylate ester and hydroxyadamantyl (meth) acrylate ester. Among these, (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, and (meth) acrylic acid propyl ester are preferable from the viewpoints of heat resistance and alkali developability. These monomers can be used alone or in combination of two or more.

  The component (A) includes, for example, a monomer obtained by protecting the hydroxyl group of the monomer represented by the general formula (7) with a protecting group such as a t-butyl group or an acetyl group, and the monomer represented by the general formula (8). The copolymer obtained by the polymerization reaction can be formed by a known method, for example, by deprotecting under an acid catalyst and converting it into a hydroxystyrene-based structural unit.

  Specifically, for example, it can be synthesized by the following method. A reaction solvent such as propylene glycol monomethyl ether is weighed into a three-necked flask equipped with a stirrer, a nitrogen introducing tube and a thermometer, and separately weighed polymerizable monomer and azobisisobutyronitrile (AIBN) are added. . While stirring at room temperature, nitrogen gas is flowed to remove dissolved oxygen. Thereafter, the inflow of nitrogen gas is stopped, the flask is sealed, and the temperature is raised in a constant temperature water bath to carry out a polymerization reaction. After completion of the reaction, the flask is cooled, and purified water and hydrochloric acid are added and stirred for deprotection. Thereafter, the resin solution is dropped into a large amount of water, and the obtained solid is filtered under reduced pressure. Then, the obtained solid is dissolved again in the reaction solvent, dropped again into a large amount of water, filtered under reduced pressure, and the obtained solid is vacuum-dried to obtain the target product.

  The content of the structural unit represented by the general formula (1) in the component (A) is 10% with respect to all structural units in the copolymer from the viewpoint of solubility in an alkaline developer in the exposed area and adhesiveness. -99 mol% is preferable, 20-97 mol% is more preferable, 30-95 mol% is still more preferable.

  The content of the structural unit represented by the general formula (2) in the component (A) is the total structure in the copolymer from the viewpoints of dissolution inhibition with respect to the alkaline developer in the unexposed area, adhesiveness, and cured film physical properties. 1-90 mol% is preferable with respect to a unit, 3-80 mol% is more preferable, 5-70 mol% is still more preferable.

  The ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the component (A) is a molar ratio, and (1) :( 2) = 10: 90 to 99: 1 is preferable, (1) :( 2) = 20: 80 to 97: 3 is more preferable, and (1) :( 2) = 30: 70 to 95: 5 is preferable. Further preferred.

  The molecular weight of the component (A) is preferably 1,000 to 500,000, preferably 2,000 to 200,000 in terms of weight average molecular weight, considering the solubility in aqueous alkali solution and the balance between the photosensitive properties and the cured film properties. More preferably, it is 2,000-100,000. Here, the weight average molecular weight is a value obtained by measuring by a gel permeation chromatography (GPC) method and converting from a standard polystyrene calibration curve.

  Although there is no restriction | limiting in particular in content of (A) component in a resin composition, It is preferable that it is 30-80 mass% with respect to the whole resin composition from a viewpoint of a cured film physical property, and it is 35-75 mass%. It is more preferable, and it is still more preferable that it is 40-70 mass%.

<(B) component: Compound that generates acid by light>
The resin composition of this embodiment contains (B) the compound which produces | generates an acid by light. The component (B) is used as a photosensitizer in the resin composition. Such a component (B) has a function of generating acid upon irradiation with light and increasing the solubility of the irradiated portion in an alkaline aqueous solution.

  As the component (B), a compound generally called a photoacid generator can be used. Specific examples of the component (B) include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. (B) A component may consist only of 1 type in these compounds, and may be comprised including 2 or more types. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  As the o-quinonediazide compound, for example, a compound obtained by subjecting o-quinonediazidesulfonyl chloride to a hydroxy compound and / or an amino compound in the presence of a dehydrochlorinating agent can be used.

  Examples of the o-quinonediazidosulfonyl chloride used in the reaction include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-6. A sulfonyl chloride is mentioned.

  Examples of the hydroxy compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- ( 4-hydroxyphenyl) -1-methylethyl} phenyl] ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetra Hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,2', 3'-pentahydroxybenzophenone, 2,3,4,3 ', 4', 5'-hexahydroxy Benzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydro Xylphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindeno [2,1-a] indene, tris (4-hydroxyphenyl) methane, And tris (4-hydroxyphenyl) ethane.

  Examples of the amino compound used in the reaction include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4 ′. -Diaminodiphenyl sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) Sulfone, bis (3-amino-4-hydroxyphenyl) Examples include xafluoropropane and bis (4-amino-3-hydroxyphenyl) hexafluoropropane.

  Among these, from the absorption wavelength range and reactivity, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane and 1 -Naphthoquinone-2-diazide-5-sulfonyl chloride obtained by condensation reaction, tris (4-hydroxyphenyl) methane or tris (4-hydroxyphenyl) ethane and 1-naphthoquinone-2-diazide-5 -It is preferable to use what was obtained by condensation reaction with sulfonyl chloride.

  Examples of the dehydrochlorinating agent used in the reaction include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine. Examples of the reaction solvent include dioxane, acetone, methyl ethyl ketone, tetrahydrofuran (THF), diethyl ether, and N-methylpyrrolidone.

  o-quinonediazidosulfonyl chloride and hydroxy compound and / or amino compound are blended so that the total number of moles of hydroxy group and amino group is 0.5 to 1 per mole of o-quinonediazidesulfonyl chloride. It is preferred that A preferred blending ratio of the dehydrochlorinating agent and o-quinonediazide sulfonyl chloride is in the range of 0.95 / 1 molar equivalent to 1 / 0.95 molar equivalent.

  In addition, the preferable reaction temperature of the above-mentioned condensation reaction is 0-40 degreeC, and preferable reaction time is 1 to 10 hours.

  The content of the component (B) in the resin composition is 3 to 100 mass with respect to 100 parts by mass of the component (A) because the difference in dissolution rate between the exposed part and the unexposed part increases and the sensitivity becomes better. Part, preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight, and particularly preferably 5 to 20 parts by weight.

<(C) component)>
The resin composition of the present embodiment contains (C) a thermal crosslinking agent. The component (C) is a compound having a structure that can react with the component (A) to form a bridge structure when the patterned resin film is cured by heating. Thereby, brittleness of the film and melting of the film can be prevented. The thermal crosslinking agent is preferably selected from, for example, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and a compound having an epoxy group.

  The “compound having a phenolic hydroxyl group” here does not include an alkali-soluble copolymer as the component (A). The compound having a phenolic hydroxyl group as a thermal crosslinking agent can increase the dissolution rate of the exposed area when developing with an alkaline aqueous solution as well as the thermal crosslinking agent, and improve the sensitivity. The molecular weight of such a compound having a phenolic hydroxyl group is preferably 2000 or less. In consideration of the solubility in an aqueous alkali solution and the balance between the photosensitive properties and the mechanical properties, the number average molecular weight is preferably 94 to 2000, more preferably 108 to 2000, and particularly preferably 108 to 1500.

  As the compound having a phenolic hydroxyl group, conventionally known compounds can be used, but the compound represented by the following general formula (9) prevents dissolution at the time of curing the resin film and the effect of promoting dissolution of the exposed portion. It is excellent in the balance of the effect and is preferable.

［式（９）中、Ｘは単結合又は２価の有機基を示し、Ｒ^６、Ｒ^７、Ｒ^８及びＲ^９はそれぞれ独立に水素原子又は１価の有機基を示し、ｓ及びｔはそれぞれ独立に１〜３の整数を示し、ｕ及びｖはそれぞれ独立に０〜４の整数を示す。］

[In formula (9), X represents a single bond or a divalent organic group, R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or a monovalent organic group, and s and t are Each independently represents an integer of 1 to 3, and u and v each independently represent an integer of 0 to 4. ]

  In the general formula (9), examples of the compound in which X is a single bond include a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include alkylene groups having 1 to 10 carbon atoms such as methylene group, ethylene group and propylene group, alkylidene groups having 2 to 10 carbon atoms such as ethylidene group, and phenylene groups. An arylene group having 6 to 30 carbon atoms, such as a group in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom such as a fluorine atom, a sulfonyl group, a carbonyl group, an ether bond, a thioether bond, an amide bond Etc.

  Examples of the compound having a hydroxymethylamino group include (poly) (N-hydroxymethyl) melamine, (poly) (N-hydroxymethyl) glycoluril, (poly) (N-hydroxymethyl) benzoguanamine, (poly) (N- And nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups such as hydroxymethyl) urea. Here, the alkyl group of the alkyl ether includes a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specific examples include hexakis (methoxymethyl) melamine, hexakis (butoxymethyl) melamine, tetrakis (methoxymethyl) glycoluril, tetrakis (butoxymethyl) glycoluril, and tetrakis (methoxymethyl) urea.

  A conventionally well-known thing can be used as a compound which has an epoxy group. Specific examples of the compound having an epoxy group include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, glycidylamine, heterocyclic epoxy resin, Examples thereof include polyalkylene glycol diglycidyl ether.

  As component (C), in addition to the above, hydroxymethyl groups such as bis [3,4-bis (hydroxymethyl) phenyl] ether and 1,3,5-tris (1-hydroxy-1-methylethyl) benzene Aromatic compounds, compounds having maleimide groups such as bis (4-maleimidophenyl) methane and 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, compounds having a norbornene skeleton, polyfunctional acrylate compounds A compound having an oxetanyl group, a compound having a vinyl group, or a blocked isocyanate compound can be used.

  Among the components (C) described above, a compound having a phenolic hydroxyl group or a compound having a hydroxymethylamino group is preferable because sensitivity and heat resistance can be further improved. Furthermore, a compound having a hydroxymethylamino group is more preferable, and a compound having an alkoxymethylamino group obtained by alkylating all or part of the hydroxymethylamino group is more preferable from the viewpoint that the resolution and the elongation of the coating film can be further improved. A compound having an alkoxymethylamino group obtained by alkylating all hydroxymethylamino groups is particularly preferable.

  Of the compounds having an alkoxymethylamino group obtained by alkylating all of the hydroxymethylamino groups, compounds represented by the following general formula (10) are preferred.

［一般式（１０）中、Ｒ^１０〜Ｒ^１５は、それぞれ独立に炭素数１〜１０のアルキル基を示す。］

[In General Formula (10), R ^{10 to} R ¹⁵ each independently represents an alkyl group having 1 to 10 carbon atoms. ]

In the general formula (10), examples of R ^{10 to} R ¹⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. . Among these, a methyl group, an ethyl group, and a propyl group are preferable from the viewpoints of reactivity and alkali developability.

  As a process using the photosensitive adhesive composition having buffer coat characteristics, a thermocompression bonding process is performed after pattern formation. At this time, it is preferable to use at least two types of (C) thermal crosslinking agents having different reaction temperatures. These two types of thermal cross-linking agents are preferably used in combination with a thermal cross-linking agent whose reaction proceeds at a temperature lower than the pressure bonding temperature of 80 to 150 ° C. and two types of thermal cross-linking agents whose reaction proceeds at 150 to 230 ° C. .

By using the cross-linking agent in combination, semi-curing can be performed once after pattern formation, pattern deformation in the process up to pressure bonding can be prevented, and sufficient flexibility for pressure bonding can be maintained. Furthermore, the adhesive strength with the adherend can be enhanced by proceeding with the curing after the pressure bonding.
As the component (C), it is desirable to use a compound having a hydroxymethylamino group and a compound having an epoxy group in combination.

  The content of such a component (C) is preferably 2 to 25 parts by mass, more preferably 5 to 20 parts by mass, with respect to the component (A), from the viewpoint of cured film properties and alkali developability. Part by mass is more preferable.

<(D) component>
The resin composition of this embodiment contains an acrylic resin having a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4) as the component (D). When the resin composition contains the component (D), the thermal shock resistance can be improved while maintaining good photosensitive characteristics. (D) A component may consist only of 1 type of acrylic resins, and may contain 2 or more types of acrylic resins.

In general formula (3), R represents a hydrogen atom or a methyl group. In the general formula (3), ^{R 3} represents an alkyl group having 4 to 20 carbon atoms. Specific examples of R ³ include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group (sometimes referred to as lauryl group), tridecyl group, tetradecyl group. Pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and structural isomers thereof. Among these, from the viewpoint of improving sensitivity, resolution, and thermal shock, R ³ is preferably an alkyl group having 4 to 16 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms, The case of 4 alkyl groups (n-butyl group) is particularly preferred.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (3) include (meth) acrylic acid alkyl esters. Examples of the (meth) acrylic acid alkyl ester include compounds represented by the following general formula (11).

［一般式（１１）中、Ｒ、Ｒ^３はそれぞれ一般式（３）におけるＲ、Ｒ^３と同じ意味である。］

[In General Formula (11), R and R ³ have the same meanings as R and R ³ in General Formula (3), respectively. ]

  Examples of the polymerizable monomer represented by the general formula (11) include (meth) acrylic acid butyl ester, (meth) acrylic acid pentyl ester, (meth) acrylic acid hexyl ester, and (meth) acrylic acid heptyl. Ester, (Meth) acrylic acid octyl ester, (Meth) acrylic acid nonyl ester, (Meth) acrylic acid decyl ester, (Meth) acrylic acid undecyl ester, (Meth) acrylic acid dodecyl ester ((Meth) acrylic acid lauryl ester (Meth) acrylic acid tridecyl ester, (meth) acrylic acid tetradecyl ester, (meth) acrylic acid pentadecyl ester, (meth) acrylic acid hexadecyl ester, (meth) acrylic acid heptadecyl ester , Octadecyl Este (meth) acrylate , (Meth) acrylic acid nonadecyl ester, and (meth) acrylic acid eicosyl ester. These polymerizable monomers can be used alone or in combination of two or more.

  In the component (D), the composition ratio of the structural unit represented by the general formula (3) is preferably 50 to 93 mol% with respect to the total amount of the structural units in the component (D). It is more preferably 85 mol%, and particularly preferably 60 to 80 mol%. When the composition ratio of the structural unit represented by the general formula (3) is within the above range, the thermal shock resistance of the cured film of the resin composition can be further improved.

  Moreover, (D) component contains the structural unit represented by General formula (4). Thereby, compatibility with (D) component and (A) component improves, and the adhesiveness to the board | substrate of a pattern cured film, a mechanical characteristic, and a thermal shock resistance can be improved more.

Examples of the hydroxyalkyl group having 2 to 20 carbon atoms represented by R ⁴ in the general formula (4) include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, Hydroxyoctyl group, hydroxynonyl group, hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group (sometimes referred to as hydroxylauryl group), hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, Examples include hydroxyheptadecyl group, hydroxyoctadecyl group, hydroxynonadecyl group, hydroxyeicosyl group and structural isomers thereof.

Further, in the general formula (4), R ⁴ is preferably a hydroxyalkyl group having 2 to 20 carbon atoms, and a hydroxyalkyl group having 2 to 15 carbon atoms, from the viewpoint of improving compatibility with the component (A) and improving thermal shock. Group is more preferable, and a hydroxyalkyl group having 2 to 10 carbon atoms is particularly preferable.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (4) include (meth) acrylic acid hydroxyalkyl ester represented by the following general formula (12).

［一般式（１２）中、Ｒ、Ｒ^４はそれぞれ一般式（４）におけるＲ、Ｒ^４と同じ意味である。］

[In General Formula (12), R and R ⁴ have the same meanings as R and R ⁴ in General Formula (4), respectively. ]

  Examples of the polymerizable monomer represented by the general formula (12) include (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester, (meth) acrylic acid hydroxybutyl ester, (meth) Acrylic acid hydroxypentyl ester, (meth) acrylic acid hydroxyhexyl ester, (meth) acrylic acid hydroxyheptyl ester, (meth) acrylic acid hydroxyoctyl ester, (meth) acrylic acid hydroxynonyl ester, (meth) acrylic acid hydroxydecyl ester , (Meth) acrylic acid hydroxyundecyl ester, (meth) acrylic acid hydroxydodecyl ester (sometimes referred to as (meth) acrylic acid hydroxylauryl ester), (meth) acrylic acid hydroxytridecyl ester (Meth) acrylic acid hydroxytetradecyl ester, (meth) acrylic acid hydroxypentadecyl ester, (meth) acrylic acid hydroxyhexadecyl ester, (meth) acrylic acid hydroxyheptadecyl ester, (meth) acrylic acid hydroxyoctadecyl ester, Examples include (meth) acrylic acid hydroxynonadecyl ester and (meth) acrylic acid hydroxyeicosyl ester. These polymerizable monomers can be used alone or in combination of two or more.

  In the component (D), the composition ratio of the structural unit represented by the general formula (4) is preferably 0.1 to 40 mol% with respect to the total amount of the structural units in the component (D). It is more preferably 0.3 to 35 mol%, and particularly preferably 0.5 to 30 mol%. When the composition ratio of the structural unit represented by the general formula (4) is within the above range, the compatibility between the component (D) and the component (A) and the thermal shock resistance of the cured film obtained from the resin composition are improved. It can be improved.

  In view of providing higher sensitivity, the component (D) preferably further has a structural unit represented by the following general formula (5).

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (5) include acrylic acid and methacrylic acid.

  When the component (D) has a structural unit represented by the general formula (5), the composition ratio of the structural unit is 5 to 35 mol% with respect to the total amount of the structural unit in the component (D). Is more preferable, 10 to 30 mol% is more preferable, and 15 to 25 mol% is particularly preferable. When the composition ratio of the structural unit represented by the general formula (5) is within the above range, the compatibility with the component (A) and the sensitivity and developability of the resin composition can be further improved.

  It is preferable that the component (D) further has a structural unit represented by the following general formula (6) from the viewpoint of further improving the dissolution inhibition property of the unexposed portion in the developer.

In general formula (6), R ⁵ represents a monovalent organic group having a primary, secondary, or tertiary amino group. Specific examples of R ⁵ include aminoethyl group, N-methylaminoethyl group, N, N-dimethylaminoethyl group, N-ethylaminoethyl group, N, N-diethylaminoethyl group, aminopropyl group, N-methyl. Examples thereof include an aminopropyl group, an N, N-dimethylaminopropyl group, an N-ethylaminopropyl group, an N, N-diethylaminopropyl group, and a monovalent organic group represented by the following general formula (13). Among these, in particular, R ⁵ is represented by the following general formula (13) in the general formula (6) from the viewpoint that the adhesiveness of the patterned cured film to the substrate, mechanical properties, and thermal shock resistance can be further improved. The organic group is particularly preferable.

［一般式（１３）中、Ｘは炭素数１〜５のアルキレン基を示し、Ｒ^１７〜Ｒ^２１は各々独立に水素原子又は炭素数１〜２０のアルキル基を示す。ｎは０〜１０の整数を示す。］

[In General Formula (13), X represents an alkylene group having 1 to 5 carbon atoms, and R ^{17 to} R ²¹ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n represents an integer of 0 to 10. ]

In the general formula (13), specific examples of X include methylene, ethylene, propylene, and the like. Specific examples of R ^{17 to} R ²¹ include a hydrogen atom, a methyl group, an ethyl group, and a propylene group. From the viewpoint of improving the cured film properties and heat resistance, n is preferably 1 to 5.

  Specific examples of the group represented by the general formula (13) include piperidin-4-yl group, 1-methylpiperidin-4-yl group, 2,2,6,6-tetramethylpiperidin-4-yl. Group, 1,2,2,6,6-pentamethylpiperidin-4-yl group, (piperidin-4-yl) methyl group, 2- (piperidin-4-yl) ethyl group.

  Examples of the polymerizable monomer that gives the structural unit represented by the general formula (6) include compounds represented by the following general formula (14).

［一般式（１４）中、Ｒ、Ｒ^５はそれぞれ一般式（６）におけるＲ、Ｒ^５と同じ意味である。］

[In General Formula (14), R and R ⁵ have the same meanings as R and R ⁵ in General Formula (6), respectively. ]

Examples of the polymerizable monomer represented by the general formula (14) include aminoethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N- Ethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N- Examples include ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, and a polymerizable monomer in which R ⁵ is a monovalent organic group represented by the general formula (12). These polymerizable monomers can be used alone or in combination of two or more.

Examples of the polymerizable monomer in which R ⁵ is represented by the general formula (13) include piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2,6 , 6-tetramethylpiperidin-4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate, 2- (piperidin-4-yl) ethyl (meth) acrylate is mentioned. Among these, 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate is FA-711MM, and 2,2,6,6-tetramethylpiperidin-4-yl methacrylate is FA-712HM. (Both manufactured by Hitachi Chemical Co., Ltd.) are preferable because they are commercially available.

  In the component (D), the composition ratio of the structural unit represented by the general formula (6) is based on the total amount of the component (D) from the viewpoint of compatibility with the component (A) and solubility in the developer. 0.3 to 10 mol% is preferable, 0.4 to 6 mol% is more preferable, and 0.5 to 5 mol% is particularly preferable.

  The acrylic resin includes, for example, a polymerizable monomer that gives a structural unit represented by the general formulas (3) and (4), and optionally a structure represented by the general formulas (5) and (6). It can be obtained by stirring a polymerizable monomer giving a unit in a solvent such as toluene or isopropanol, and heating as necessary.

  Moreover, the polymerizable monomer used for the synthesis | combination of the said acrylic resin is other than the polymerizable monomer which gives each structural unit represented by General formula (3), (4), (5) and (6). It may further contain a polymerizable monomer.

  Examples of the polymerizable monomer other than the polymerizable monomer that gives each structural unit represented by the general formulas (3), (4), (5), and (6) include styrene, α-methylstyrene, (Meth) acrylic acid benzyl ester, (meth) acrylic acid 4-methylbenzyl ester, acrylonitrile, esters of vinyl alcohol such as vinyl-n-butyl ether, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid glycidyl Ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, maleic acid Examples include maleic acid monoesters such as nomethyl, monoethyl maleate and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These polymerizable monomers are used alone or in combination of two or more.

  In particular, when a (meth) acrylic acid glycidyl ester having a group capable of crosslinking with the component (A) is included, it is preferable because mechanical properties such as elongation at break are further improved.

  (D) It is preferable that the weight average molecular weights of a component are 2000-100000, It is more preferable that it is 3000-60000, It is especially preferable that it is 5000-50000, It is most preferable that it is 10000-40000. When the weight average molecular weight is 2000 or more, the thermal shock resistance of the cured film can be further improved, and when it is 100000 or less, compatibility with the component (A) and developability can be further improved.

  The content of the component (D) is preferably 1 to 50 parts by weight, and 3 to 30 parts by weight with respect to 100 parts by weight of the total amount of the component (A) from the viewpoint of sensitivity, resolution, adhesion, mechanical properties, and thermal shock resistance. Part is more preferable, and 5 to 20 parts by mass is particularly preferable.

  A solvent can be used for the resin composition according to the present embodiment. Since the resin composition contains a solvent, it is preferable because it facilitates application on a substrate and easily forms a coating film having a uniform thickness. Examples of the solvent include γ-butyrolactone, ethyl lactate, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2- Pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethyl phosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether , Propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more.

  Moreover, the content of the solvent in the resin composition is not particularly limited, but is preferably adjusted so that the ratio of the solvent in the resin composition is 20 to 90% by weight.

<Other ingredients>
In addition to the above components (A) to (D), the resin composition described above is an elastomer, a compound that generates an acid upon heating, a dissolution accelerator, a dissolution inhibitor, a coupling agent, and a surfactant or leveling agent. These components may be contained.

(Elastomer)
Examples of the elastomer include a styrene elastomer, an olefin elastomer, a urethane elastomer, a polyester elastomer, a polyamide elastomer, and a silicone elastomer. The elastomer may be a fine particle elastomer. These elastomers can be used alone or in combination of two or more.

(Compound that generates acid by heating)
By using a compound that generates an acid by heating, it becomes possible to generate an acid when the resin film obtained from the resin composition of the present embodiment is heated, and the reaction between the component (A) and the component (C) That is, the thermal crosslinking reaction is promoted, and the heat resistance of the cured film is improved. Moreover, since the compound which produces | generates an acid by heating generate | occur | produces an acid also by light irradiation, the solubility to the alkaline aqueous solution of an exposure part increases. Therefore, the difference in solubility in the alkaline aqueous solution between the unexposed area and the exposed area is further increased, and the resolution is improved.

  It is preferable that the compound which produces | generates an acid by such a heating is what produces | generates an acid by heating to 50-250 degreeC, for example. Specific examples of the compound that generates an acid by heating include a salt formed from a strong acid such as an onium salt and a base, and imide sulfonate.

  Examples of the onium salt include diaryliodonium salts such as aryldiazonium salts and diphenyliodonium salts; di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; trialkylsulfonium salts such as trimethylsulfonium salts; Examples include dialkyl monoaryl sulfonium salts such as dimethylphenylsulfonium salt; diaryl monoalkyl iodonium salts such as diphenylmethylsulfonium salt; triarylsulfonium salts and the like. Among these, di (t-butylphenyl) iodonium salt of paratoluenesulfonic acid, di (t-butylphenyl) iodonium salt of trifluoromethanesulfonic acid, trimethylsulfonium salt of trifluoromethanesulfonic acid, dimethyl of trifluoromethanesulfonic acid Phenylsulfonium salt, diphenylmethylsulfonium salt of trifluoromethanesulfonic acid, di (t-butylphenyl) iodonium salt of nonafluorobutanesulfonic acid, diphenyliodonium salt of camphorsulfonic acid, diphenyliodonium salt of ethanesulfonic acid, benzenesulfonic acid Dimethylphenylsulfonium salt and diphenylmethylsulfonium salt of toluenesulfonic acid are preferred.

  Moreover, as a salt formed from a strong acid and a base, the salt formed from the following strong acids and a base other than the above-mentioned onium salt, for example, a pyridinium salt can also be used. Examples of the strong acid include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, perfluoroalkylsulfonic acid such as nonafluorobutanesulfonic acid, methanesulfonic acid, and ethane. Examples thereof include alkylsulfonic acids such as sulfonic acid and butanesulfonic acid. Examples of the base include pyridine, alkylpyridines such as 2,4,6-trimethylpyridine, N-alkylpyridines such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridines.

  As the imide sulfonate, for example, naphthoyl imide sulfonate or phthalimide sulfonate can be used.

Moreover, as a compound which produces | generates an acid by heating, the compound which has the structure represented by following General formula (15) other than the above-mentioned, and the sulfonamide structure represented by following General formula (16) is used. You can also.
R ²² R ²³ C═N—O—SO ₂ —R ²⁴ (15)
—NH—SO ₂ —R ²⁵ (16)

In the formula (11), R ²² is, for example, a cyano group, and R ²³ is, for example, a methoxyphenyl group or a phenyl group. R ²⁴ is, for example, an aryl group such as p-methylphenyl group or phenyl group, an alkyl group such as methyl group, ethyl group or isopropyl group, or a perfluoroalkyl group such as trifluoromethyl group or nonafluorobutyl group. is there.

In the formula (16), R ²⁵ is, for example, an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a methylphenyl group or a phenyl group, a perfluoroalkyl group such as a trifluoromethyl group or nonafluorobutyl. It is. Examples of the group bonded to the N atom of the sulfonamide structure represented by the general formula (16) include 2,2′-bis (4-hydroxyphenyl) hexafluoropropane and 2,2′-bis (4-hydroxy). Phenyl) propane, di (4-hydroxyphenyl) ether.

  When using the compound which produces | generates an acid by heating, 0.1-30 mass parts is preferable with respect to 100 mass parts of (A) component, 0.2-20 mass parts is more preferable, 0.5 10 parts by mass is particularly preferable.

(Dissolution promoter)
By blending the dissolution accelerator in the resin composition of the present embodiment, the dissolution rate of the exposed area when developing with an alkaline aqueous solution can be increased, and the sensitivity and resolution can be improved. A conventionally well-known thing can be used as a dissolution promoter. Specific examples thereof include compounds having a carboxyl group, a sulfonic acid, and a sulfonamide group.

  The content in the case of using such a dissolution accelerator can be determined by the dissolution rate with respect to the aqueous alkali solution, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of component (A). .

(Dissolution inhibitor)
A dissolution inhibitor is a compound that inhibits the solubility of the component (A) in an alkaline aqueous solution, and is used to control the remaining film thickness, development time, and contrast. Specific examples thereof include diphenyliodonium nitrate, bis (p-tert-butylphenyl) iodonium nitrate, diphenyliodonium bromide, diphenyliodonium chloride, and diphenyliodonium iodide. In the case of using a dissolution inhibitor, the content is preferably 0.01 to 20 parts by mass, and 0.01 to 15 parts by mass with respect to 100 parts by mass of component (A), from the viewpoint of sensitivity and the allowable range of development time. More preferred is 0.05 to 10 parts by mass.

(Coupling agent)
By mix | blending a coupling agent with the above-mentioned resin composition, the adhesiveness with the board | substrate of the cured film formed can be improved. Examples of the coupling agent include organic silane compounds and aluminum chelate compounds.

  Examples of the organic silane compound include vinyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, n- Propylphenylsilanediol, isopropylphenylsilanediol, n-butylsiphenylsilanediol, isobutylphenylsilanediol, tert-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol , N-butylmethylphenylsilanol, isobutylmethylphenylsilanol, tert-butylmethylphenylsilanol , Ethyl n-propylphenylsilanol, ethylisopropylphenylsilanol, n-butylethylphenylsilanol, isobutylethylphenylsilanol, tert-butylethylphenylsilanol, methyldiphenylsilanol, ethyldiphenylsilanol, n-propyldiphenylsilanol, isopropyldiphenylsilanol , N-butyldiphenylsilanol, isobutyldiphenylsilanol, tert-butyldiphenylsilanol, phenylsilanetriol, 1,4-bis (trihydroxysilyl) benzene, 1,4-bis (methyldihydroxysilyl) benzene, 1,4-bis (Ethyldihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldi) Droxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropyldroxysilyl) benzene, 1,4-bis (dibutylhydroxy) Silyl) benzene.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of using a coupling agent, 0.5-10 mass parts is more preferable.

(Surfactant or leveling agent)
By blending a surfactant or a leveling agent in the resin composition of the present embodiment, it is possible to improve applicability, for example, to prevent striation (film thickness unevenness) or to improve developability. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like. Commercially available products include F171, F173, R-08 (manufactured by DIC Corporation, trade name), FLORARD FC430, FC431 (manufactured by Sumitomo 3M Corporation, trade name), organosiloxane polymers KP341, KBM303, KBM403, KBM803 (Shin-Etsu Chemical). Kogyo Co., Ltd., trade name).

  0.001-5 mass parts is preferable with respect to 100 mass parts of (A) component, and, as for content in the case of using surfactant or a leveling agent, 0.01-3 mass parts is more preferable.

  The photosensitive adhesive composition having a buffer coat property can be developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH). Furthermore, by using the photosensitive adhesive composition having the above-mentioned buffer coating properties, it is possible to form a patterned cured film having good adhesion and crack resistance in a thermal shock cycle. Moreover, the pattern cured film which consists of the photosensitive adhesive composition which has the buffer coat characteristic of this invention has a favorable photosensitive characteristic (sensitivity and resolution), and has sufficient mechanical characteristics (break elongation and elastic modulus). .

<Method for Manufacturing Semiconductor Device>
Next, a method for manufacturing a semiconductor device using the photosensitive adhesive composition having the above-described buffer coat characteristics will be described.

The manufacturing method according to this embodiment mainly includes the following steps.
Step 1: A step of applying a photosensitive adhesive composition to a circuit surface of a semiconductor wafer and drying to form a photosensitive adhesive composition film.
Step 2: A step of exposing a predetermined portion of the photosensitive adhesive composition film.
Step 3: A step of forming a desired pattern by developing the photosensitive adhesive composition film after exposure and removing the predetermined portion.
Step 4: A step of heating the semiconductor wafer on which the pattern is formed to remove the residual solvent.
Step 5: A step of performing an ashing process after removing the insulating film in the predetermined portion of the photosensitive adhesive composition film by etching.
Step 6: A step of thinning the wafer and dividing the chip into individual pieces.
Step 7: A step of stacking chips.
Step 8: A step of heat-curing the adhesive layer.
Hereinafter, each step will be described.

Step 1: Application and drying A photosensitive adhesive composition is applied to the circuit surface of a semiconductor wafer. For coating, the coating method is selected from a printing method, a spin coating method, a spray coating method, a jet dispensing method, an inkjet method, and the like. Among these, the spin coat method is preferable from the viewpoint of thinning and film thickness uniformity. Application by spin coating is preferably performed at a rotational speed of 500 to 5000 min ⁻¹ in order to prevent wafer undulation and edge swell. From the same viewpoint, the rotational speed is more preferably 600 to 4000 min ⁻¹ . From the viewpoint of the dissolution rate of the exposed area in the developer, the remaining film ratio of the unexposed area and the sensitivity, the drying is preferably 80 to 150 ° C. From the same viewpoint, drying is more preferably 100 to 130 ° C.

  When a photosensitive adhesive composition is applied to a semiconductor wafer by, for example, a spin coating method, an unnecessary photosensitive adhesive composition may adhere to the edge portion of the semiconductor wafer. Such unnecessary adhesive can be removed by washing with a solvent after spin coating. The cleaning method is not particularly limited, but a method of discharging a solvent from a nozzle to a portion where an unnecessary adhesive is attached while spinning a semiconductor wafer is preferable. The solvent used for the cleaning may be any solvent that dissolves the adhesive. For example, a low boiling point solvent selected from methyl ethyl ketone, acetone, isopropyl alcohol and methanol, DMF (N, N-dimethylformamide), NMP (N-methyl- A high boiling point solvent such as 2-pyrrolidone) is used.

  After the photosensitive adhesive composition is applied to the semiconductor wafer, the photosensitive adhesive layer is formed by drying using a hot plate or an oven.

Step 2: Exposure The adhesive layer composed of the applied photosensitive adhesive composition is irradiated with actinic rays (typically ultraviolet rays) by an exposure device to expose the adhesive layer. The exposure is performed for the purpose of forming an adhesive pattern on the adhesive layer. In the present embodiment, a predetermined pattern is provided so that the dicing line portion when the semiconductor wafer is divided into a plurality of semiconductor chips and the adhesive layer of the bonding pad portion for wire bonding are removed by development. Exposure is performed through a mask.
The exposure can be performed under an atmosphere such as vacuum, nitrogen, air, or the like. The exposure amount is preferably 50 to 2000 mJ / cm ² .

  The film thickness of the adhesive layer is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less.

Step 3: Adhesive pattern formation The exposed adhesive layer is developed, and the above-mentioned dicing line part and the adhesive layer of the part to be electrically connected (bonding pad part) are removed and separated into pieces. An adhesive layer (adhesive pattern) is formed. Development is performed using an alkali developer or an organic solvent. Examples of the alkali developer include alkaline aqueous solutions such as alkali metal carbonates, alkali metal hydroxides, and tetraammonium hydroxide (tetramethylammonium hydride). Examples of the organic solvent include DMF and NMP. In this way, by removing the adhesive layer of the dicing line portion and bonding pad portion in advance, the effect of suppressing the generation of chips during dicing or suppressing poor connection during wire bonding is obtained. It is done.

Step 4: Half cure The substrate on which the adhesive layer has been formed is heated to remove the remaining solvent, and the reaction of the crosslinking agent proceeds partially. The heating temperature at this time is usually 70 to 200 ° C., preferably 75 to 190 ° C., and the heating time is 1 to 60 minutes, preferably 5 to 50 minutes. By removing the solvent remaining by this heating, gas generation at the time of pressure bonding and curing described later can be suppressed, and good pressure bonding properties can be obtained. Moreover, the damage of the adhesive layer at the time of etching and ashing in step 5 can be suppressed by causing the reaction of the crosslinking agent to partially proceed by this heating.

Step 5: Etching Etching is performed using the pattern of the adhesive layer as a mask. Examples of the insulating film to be etched include SiO ₂ and SiN. Thereby, after forming a pattern using a resist on the upper part of a conventionally used adhesive layer, etching is performed using the resist as a mask, and the process of peeling the resist can be simplified. For the etching, dry etching means using a gas such as oxygen or a carbon tetrafluoride layer can be used.

Step 6: Wafer thinning and chip singulation When the substrate having the adhesive layer is singulated, a “first dicing method” in which the substrate is half-cut and then polished (back grind) to a desired substrate thickness, or There is a method in which dicing is performed after the substrate is first polished (back grind) to a desired thickness.
When dicing is performed, since the dicing is performed with the adhesive layer surface as a surface, it is exposed to cooling water during the dicing process. For this reason, the adhesive layer is preferably a material having a low water absorption rate. If the adhesive layer absorbs water during the dicing process, it becomes a degassing factor in the press-bonding process and the curing process described later.

Step 7: Pressure bonding The adherend is pressure bonded to the adhesive layer surface of the substrate having the patterned adhesive layer. The treatment temperature in the pressure bonding step is 100 to 200 ° C., the pressure is 0.01 to 5 MPa, and the treatment time is 0.5 to 120 seconds.

  The tack strength (surface tack force) at a pressure treatment temperature of 100 to 200 ° C. on the surface of the adhesive layer after exposure and development is preferably 100 gf or less. Thereby, it can fully suppress that an adhesive bond adheres to a collet at the time of pick-up, and when carrying out lamination of a plurality of semiconductor chips and producing a semiconductor device, continuous press-fit becomes possible. The tack strength is more preferably 100 gf or less, and still more preferably 80 gf or less, because the above effects can be obtained more sufficiently. Moreover, since it becomes easy to laminate | stack a several semiconductor chip, it is preferable that tack intensity | strength is 5 gf or more.

  The tack strength of the adhesive layer surface is measured as follows. First, an adhesive layer made of a photosensitive adhesive composition is formed on a silicon wafer using a spin coater so as to have a film thickness of 10 μm. Then, after heating at 150 ° C./10 minutes using a hot plate, the tack strength of the adhesive composition layer surface at a predetermined temperature (for example, 120 ° C.) is measured using a probe tacking tester manufactured by Reska Co., Ltd. Measurement is performed under the conditions of probe diameter: 5.1 mm, peeling speed: 5 mm / s, contact load: 0.2 MPa, and contact time: 1 s.

  The tack strength (surface tack force) at 120 to 180 ° C. on the surface of the adhesive composition layer is preferably 80 gf or more, and more preferably 50 gf or more. If the tack strength is 80 gf or more, collet adhesion may occur during thermocompression bonding.

Process 8: Curing After pressure-bonding the adherend to the adhesive composition surface, heat treatment is performed at 150 to 200 ° C. for 1 to 9 hours.

FIG. 1 shows an example of a semiconductor device formed using the photosensitive adhesive composition of the present invention.
In the semiconductor device shown in FIG. 1, the semiconductor chip 2 separated into a support member (semiconductor element mounting support member) 13 for a semiconductor device is laminated via an adhesive member 30, and a semiconductor is further formed on the semiconductor chip 2. The chip 2 is repeatedly laminated through the photosensitive adhesive layer 5 made of the photosensitive adhesive composition of the present invention to obtain a multilayer structure in which a plurality of semiconductor chips are laminated, and the photosensitive adhesive layer 5 is cured. Do. Then, the bonding pads 17 exposed in the openings 51 of the semiconductor chip 2 and the external connection terminals 16 of the semiconductor device support member (semiconductor element mounting support member) 13 are electrically connected via the wires 14. Thereafter, the semiconductor chip 2 is sealed with the sealing material 15 to obtain the semiconductor device 120.

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

  First, the materials used in this example are shown below.

[(A) component]
A1: Copolymer of 4-hydroxystyrene / methyl methacrylate = 50/50 (molar ratio) (polystyrene equivalent weight average molecular weight = 10000, manufactured by Maruzen Petrochemical Co., Ltd., trade name “CMM”)
A2: homopolymer composed of p-hydroxystyrene, polystyrene-converted weight average molecular weight = 10000, manufactured by Toho Chemical Co., Ltd., trade name “H100”
A3: Copolymer consisting of p-hydroxystyrene / styrene = 85/15 (mol), polystyrene equivalent weight average molecular weight = 10000, manufactured by Toho Chemical Co., Ltd., trade name “C100A15”

[Component (B)]
B1: 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1-naphthoquinone-2-diazide-5-sulfonic acid Esters (Esterification rate of about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”)

[Component (C)]
C1: Hexakis (methoxymethyl) melamine represented by the following formula (17) (trade name “MW-30HM” manufactured by Sanwa Chemical Co., Ltd.)
C2: Polyethylene glycol glycidyl ether represented by the following formula (18) (manufactured by Kyoeisha Chemical Co., Ltd., trade name “Epolite 400E”, n (average value) = 9)

[(D) component]
Synthesis Example 1: Synthesis of acrylic resin D1 55 g of ethyl lactate was weighed in a 100 ml three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer, and separately weighed polymerizable monomer (acrylic acid butyl ester ( BA) 35.8 g, acrylic acid (AA) 2.6 g, acrylic acid hydroxybutyl ester (HBA) 5.2 g and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: FA -711MM, manufactured by Hitachi Chemical Co., Ltd.) 1.7 g) and azobisisobutyronitrile (AIBN) 0.29 g were added. While stirring at room temperature at a stirring speed of about 160 min ⁻¹ , nitrogen gas was passed at a flow rate of 400 ml / min for 30 minutes to remove dissolved oxygen. Thereafter, the inflow of nitrogen gas was stopped, the flask was sealed, and the temperature was raised to 65 ° C. in about 25 minutes in a constant temperature water bath. A polymerization reaction was carried out while maintaining the same temperature for 10 hours to obtain an acrylic resin D1. The polymerization rate at this time was 99%. Moreover, the weight average molecular weight (MW) of D1 was about 20000. The weight average molecular weight was determined by GPC standard polystyrene conversion.

Synthesis Example 2: Synthesis of acrylic resin D2 An acrylic resin D2 was synthesized in the same manner as in Synthesis Example 1 except that the polymerizable monomers shown in Table 1 were used. The weight average molecular weight of the synthesized acrylic resin D2 was about 20,000.

ＢＡ：アクリル酸ｎ−ブチル
ＡＡ：アクリル酸
ＨＢＡ：ヒドロキシブチルアクリレート
ＦＡ−７１１ＭＭ：１，２，２，６，６−ペンタメチルピペリジン−４−イルメタクリレート（日立化成株式会社製）

BA: n-butyl acrylate AA: acrylic acid HBA: hydroxybutyl acrylate FA-711MM: 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd.)

In addition, the weight average molecular weight of (D) component was specifically measured with the apparatus and conditions shown below.
Measuring device: Detector L-3300 RI manufactured by Hitachi, Ltd.
Pump: L-6000 manufactured by Hitachi, Ltd.
Measurement conditions: Column manufactured by Tosoh Corporation (trade name “GMH _XL- L”) × 2 Solvent: THF
Flow rate: 1.0 ml / min
It measured using the solution of 1 ml of solvent with respect to 0.5 mg of samples to measure.

<Adjustment of resin composition>
(Examples 1 to 4 and Comparative Examples 1 and 2)
Components (A) to (D) (unit: parts by mass) of the blending amounts shown in Table 2, 120 parts by mass of ethyl lactate as a solvent, and 2 parts by mass of a 50% by weight methanol solution of urea propyltriethoxysilane as a coupling agent Was pressure filtered using a PTFE (polytetrafluoroethylene) filter having a pore size of 3 μm to prepare resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2.

<Evaluation of thermocompression bonding>
A solution of the photosensitive adhesive composition is spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm, and then heated on a hot plate at 150 ° C./10 minutes. A silicon wafer with a photosensitive adhesive layer was obtained. A dicing tape (thickness: 80 μm) was laminated on the surface of the silicon wafer with an adhesive layer opposite to the adhesive layer at room temperature to prepare a dicing sample. Then, the said dicing sample which laminated | stacked the adhesive bond layer, the silicon wafer, and the dicing tape was cut | disconnected using the full auto dicer (The product made from DISCO Corporation, brand name "DFD-6361"). Cutting uses a single-cut method that completes processing with one blade (the product name “Dicing Blade NBC-ZH104F-SE 27HEDD” is used for the blade, and the blade rotation number is 45000 min ⁻¹ , cutting. The measurement was performed at a speed of 20 mm / s. The blade height at the time of cutting was set to leave 10 μm of dicing tape.
The size for cutting the semiconductor wafer was set to 3.0 mm × 3.0 mm. Next, using a thermocompression bonding machine (manufactured by Nikka Equipment Engineering Co., Ltd.), the adhesive layer of the silicon wafer with the adhesive layer diced on the silicon chip of 10 mm long × 10 mm wide × 400 μm thick is on the silicon chip side. The layers were laminated so as to come in contact with each other and pressure-bonded under conditions of 120 ° C./1 s / 5N. Then, 10 shear temperature measurements at room temperature were performed on one sample with a shear bond strength measuring device (trade name “DAGE-4000” manufactured by Dage), and a value of 0.8 MPa or more was shown. The numbers are shown in Table 2.

<Evaluation of photosensitive characteristics (sensitivity and resolution)>
A solution of the photosensitive adhesive composition was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 8 to 9 μm. Subsequently, reduction projection exposure with i-line (365 nm) was performed through a mask using an i-line stepper (trade name “FPA-3000i” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), and development was performed so that the remaining film thickness was about 80 to 95% of the initial film thickness. Then, it rinsed with water and calculated | required the magnitude | size of the minimum exposure amount required for pattern formation, and the size of the minimum square hole pattern opened. The minimum exposure amount was used as sensitivity, and the size of the smallest square hole pattern opened was evaluated as resolution. Sensitivity and resolution indicate that the smaller the value, the better.

<Evaluation of cured film properties (elongation at break and elastic modulus)>
A solution of the photosensitive adhesive composition was spin-coated on a silicon substrate and heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm. This resin film was exposed at all wavelengths through a mask using a proximity exposure machine (trade name “PLA-600FA” manufactured by Canon Inc.). After the exposure, development was performed using a 2.38% by mass aqueous solution of TMAH to obtain a pattern resin film having a 10 mm wide rectangular cross section. Thereafter, the patterned cured film was heated in nitrogen at a temperature of 175 ° C. (heating time 1.5 hours) in a vertical diffusion furnace (trade name “μ-TF” manufactured by Koyo Thermo Systems Co., Ltd.) for 4 hours. (Curing) to obtain a cured pattern film having a thickness of about 10 μm. The cured film was peeled from the silicon substrate, and the peeled cured film was used as a sample, and the elongation at break and elastic modulus were measured by “Autograph AGS-H100N” manufactured by Shimadzu Corporation. The width of the sample was 10 mm, the film thickness was about 10 μm, and the gap between chucks was 20 mm. The pulling speed was 5 mm / min, and the measurement temperature was room temperature (20 ° C. to 25 ° C.). The average of the measured values of five test pieces obtained from the cured film obtained under the same conditions was defined as elongation at break and elastic modulus. The results are shown in Table 2.

(Evaluation of stage neglectability)
A solution of the photosensitive adhesive composition is spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes to form a resin film having a thickness of about 12 to 14 μm, and then heated on a hot plate at 150 ° C./10 minutes. And a photosensitive adhesive composition film was obtained. A dicing tape (thickness 80 μm) was laminated on the surface of the silicon wafer with an adhesive layer opposite to the adhesive layer of the silicon wafer at room temperature to prepare a dicing sample. Then, the said dicing sample which laminated | stacked the adhesive bond layer, the silicon wafer, and the dicing tape was cut | disconnected using the full auto dicer (The product made from DISCO Corporation, brand name "DFD-6361"). Cutting uses a single-cut method that completes processing with one blade (the product name “Dicing Blade NBC-ZH104F-SE 27HEDD” is used for the blade, and the blade rotation number is 45000 min ⁻¹ , cutting. The measurement was performed at a speed of 20 mm / s. The blade height at the time of cutting was set to leave 10 μm of dicing tape.
The size for cutting the semiconductor wafer was set to 3.0 mm × 3.0 mm. After the diced silicon wafer with the adhesive layer is left on a hot plate at 120 ° C. for 60 minutes, using a thermocompression bonding machine (manufactured by Nikka Equipment Engineering Co., Ltd.), a silicon chip 10 mm long × 10 mm wide × 400 μm thick On top of this, the diced silicon wafer with the adhesive layer was laminated so that the adhesive layer was on the silicon chip side, and pressure bonding was performed under the condition of 120 ° C./1 s / 5N. Then, 10 shear temperature measurements at room temperature were performed on one sample with a shear bond strength measuring device (trade name “DAGE-4000” manufactured by Dage), and a value of 0.8 MPa or more was shown. The numbers are shown in Table 2.

(Tack strength at 100 to 150 ° C. of the surface of the photosensitive adhesive composition layer having buffer coating properties)
Using a probe tacking tester manufactured by Reska Co., Ltd., a silicon wafer with an adhesive layer was probe diameter: 5.1 mm, peeling speed: 10 mm / s, contact load: 200 gf / cm ² , contact time: 1 s, The tack force (adhesive strength) at a predetermined temperature was measured and used as the tack force (tack strength) on the surface of the photosensitive adhesive layer. Table 2 shows the results of evaluation of tack strength based on the following criteria.
○: 0 to 20 kgf
Δ: 20-80 kgf
X: 80 kgf or more

  Examples 1 to 4 have better photosensitivity and cured film properties than Comparative Examples 1 and 2. Furthermore, it is excellent in thermocompression bonding property and stage leaving ability.

  According to the present invention, a photosensitive adhesive composition capable of continuous pressing when forming a semiconductor device by stacking a plurality of semiconductor chips and forming a thin and high-definition adhesive pattern, and A semiconductor device manufacturing method using the same, and a semiconductor device having a photosensitive adhesive layer can be provided. Furthermore, since the photosensitive adhesive of the present invention can be cured at a low temperature, the semiconductor device can be prevented from being damaged by heat, and a highly reliable semiconductor device can be provided with high yield. The semiconductor device which has the pattern cured film which consists of a photosensitive adhesive composition of this invention as an interlayer insulation layer can be provided.

2: Separated semiconductor chip 5: Photosensitive adhesive layer 13: Support member for semiconductor device (support member for semiconductor element mounting)
14: Wire 15: Sealing material 16: External connection terminal 17: Bonding pad 30: Adhesive member 51: Opening 120: Semiconductor device

Claims (6)

(A) an alkali-soluble resin containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2);
(B) a compound that generates an acid by light;
(C) a thermal crosslinking agent;
(D) an acrylic resin having a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4);
A photosensitive adhesive composition containing:

[In General Formula (1), R represents a hydrogen atom or a methyl group, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, a represents an integer of 0 to 3, and b represents an integer of 1 to 3. In the general formula (2), R represents a hydrogen atom or a methyl group, and R ² represents a monovalent organic group. ]

[In General Formula (3), R represents a hydrogen atom or a methyl group, and R ³ represents an alkyl group having 4 to 20 carbon atoms. In the general formula (4), R represents a hydrogen atom or a methyl group, and R ⁴ represents a hydroxyalkyl group having 2 to 20 carbon atoms. ] The photosensitive adhesive composition according to claim 1, wherein the component (D) further has a structural unit represented by the following general formula (5).

[In General Formula (5), R represents a hydrogen atom or a methyl group. ] The photosensitive adhesive composition according to claim 1 or 2, wherein the component (D) further has a structural unit represented by the following general formula (6).

[In General Formula (6), R represents a hydrogen atom or a methyl group, and R ⁵ represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]   The photosensitive adhesive composition as described in any one of Claims 1-3 in which the said (B) component contains an o-quinonediazide compound. Applying and drying the photosensitive adhesive composition according to any one of claims 1 to 4 on a circuit surface of a semiconductor wafer to form a photosensitive adhesive composition film;
Exposing a predetermined portion of the photosensitive adhesive composition film; and
Developing the photosensitive adhesive composition film after the exposure to form the desired pattern by removing the predetermined portion;
Heating the semiconductor wafer on which the pattern is formed to remove residual solvent;
A step of performing an ashing process after removing the insulating film of the predetermined portion of the photosensitive adhesive composition film by etching;
A process of wafer thinning and chip separation;
A step of stacking chips;
And a step of heat-curing the adhesive layer.   A semiconductor device obtained by the manufacturing method according to claim 5.

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