JP2014202849A - Photosensitive adhesive composition, production method of pattern cured film using the same, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a photosensitive adhesive composition in which consecutive crimping can be performed and an adhesive pattern of a thin film and high-definition can be formed when two or more semiconductor chips are stacked to make a semiconductor device; a production method of a pattern cured film using the same; and an electronic component having the pattern cured film.SOLUTION: A photosensitive adhesive composition includes: (A) an alkali-soluble resin containing a phenolic hydroxyl group; (B) a compound that generates an acid by light; and (C) a heat cross-linked material. The photosensitive adhesive composition at least includes, as (C) the heat cross-linked material, 0.1-2.0 pts.mass of a compound containing an alkyl-etherified amino group represented by general formula (1), based on 100 pts.mass of (A) the alkali-soluble resin containing the phenolic hydroxyl group. In the general formula (1), R-Reach independently denote a 1-10C alkyl group.

Description

  The present invention relates to a positive photosensitive adhesive composition used for an adhesive layer or the like when laminating semiconductor devices, a method for producing a patterned cured film using the same, and an electronic component obtained by the production method.

In recent years, a semiconductor device having a multilayer structure in which a plurality of semiconductor chips are stacked has attracted attention. In a semiconductor device, a die attach film for adhering semiconductor chips is required to stack the semiconductor chips. However, the die attach film has a thickness, and since it is necessary to reduce the thickness of the semiconductor device, the thickness of the semiconductor chip itself needs to be reduced. However, this has a 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 contrast to this production method, when the conventional photosensitive resin composition for use in a low-temperature curable surface protective film shown in Patent Document 3 is used, it is crosslinked when left on a pressure-bonding stage for a long time when performing continuous pressure-bonding. The reaction of the material gradually proceeds and the adhesiveness gradually deteriorates.

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

From the above-mentioned patent documents, even if left on a pressure-bonding stage, an adhesion temperature margin is required that has excellent wet spreadability during chip lamination and enables continuous pressure bonding. Furthermore, the curing temperature of the photosensitive adhesive composition is required to have a low temperature curing characteristic of 170 to 180 ° C. in order to avoid deterioration of characteristics due to heat of the semiconductor chip.
In addition, when the positive photosensitive adhesive composition is used as a buffer coat / adhesive layer, the photosensitive resin film needs to have a certain degree of flexibility during the bonding process. It must be cured after the bonding process. Therefore, the photosensitive adhesive composition is required to have etching resistance and ashing resistance in a semi-cured state after pattern opening.
The present invention has been made in view of the above circumstances, has the same photosensitive characteristics and cured film properties as the photosensitive resin composition used as the buffer coat layer, the semi-cured film is less damaged during etching and ashing, Photosensitive adhesive composition capable of continuous pressure bonding when laminating a plurality of semiconductor chips to produce a semiconductor device and having excellent wetting and spreading properties when laminating chips, and production of a cured pattern film using the same It is an object to provide a method and an electronic component having the pattern cured film.

  In order to solve the above-mentioned problems, the present inventors based on the above-mentioned knowledge and idea, continuous pressure-bonding properties and adhesiveness at the time of thin film pattern formation, which have not been studied in conventional photosensitive resin compositions for buffer coatings. We conducted an intensive study. As a result, a photosensitive adhesive composition having the same photosensitivity and cured film physical properties as a buffer coating photosensitive resin composition, having continuous pressure bonding properties, and excellent adhesion at the time of development with a thin film, The present invention has been completed.

  That is, the present invention is a photosensitive adhesive composition containing (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, and (C) a thermal crosslinking material, 0.1 to 2.0 parts by mass of the compound having an alkyl etherified amino group represented by the following general formula (1) as a heat-crosslinking material with respect to 100 parts by mass of (A) an alkali-soluble resin having a phenolic hydroxyl group There is provided a photosensitive adhesive composition containing at least

［一般式（１）中、Ｒ^１〜Ｒ^６は、それぞれ独立に炭素数１〜１０のアルキル基を示す。］

[In the general formula ^(1), R 1 ~R ⁶ represents an alkyl group having 1 to 10 carbon atoms independently. ]

  In the photosensitive adhesive composition of the present invention, the (A) alkali-soluble resin having a phenolic hydroxyl group is preferably a phenol resin or a polyhydroxystyrene copolymer. Thereby, it has favorable continuous crimping | compression-bonding property and can improve adhesive agent pattern formation property more.

In the photosensitive adhesive composition according to the present invention, the compound (B) that generates an acid by light is preferably an o-quinonediazide compound.
The photosensitive adhesive composition according to the present invention may further contain a (D) silane compound represented by the following general formula (2).

[In General Formula (2), R ⁷ represents a divalent organic group, R ⁸ represents a monovalent organic group, and a plurality of R ⁸ in the same molecule may be the same or different. ]

  The photosensitive adhesive composition of the present invention may further contain (E) an acrylic resin.

  According to the photosensitive adhesive composition of the present invention, a semi-cured film has etching and ashing resistance, has a continuous pressure bonding property, and has an excellent wetting and spreading property during pressure bonding, a thin film and a high definition. It is possible to form a simple adhesive pattern.

The present invention also includes a step of coating and drying the photosensitive adhesive composition layer of the present invention on a substrate to form a photosensitive adhesive composition film, and a step of exposing the photosensitive adhesive composition. And developing the photosensitive adhesive composition film after exposure with an aqueous alkaline solution to form a patterned resin film, and heating the patterned resin film at 70 to 200 ° C. for 1 to 60 minutes, and then reacting A process of ion etching and plasma ashing, and bonding the substrate to the pattern resin film at 80 to 200 ° C. in 1 to 180 seconds to bond the substrate and the adherend, A manufacturing method is provided. According to this manufacturing method, a plurality of semiconductor chips can be continuously mounted, and the semiconductor device can be manufactured efficiently.
Moreover, this invention provides the electronic component which has a pattern cured film obtained by the manufacturing method of said pattern cured film.

  According to the present invention, it has excellent etching resistance and ashing resistance by semi-curing after pattern formation, and has excellent wetting and spreading properties when stacking semiconductor chips, and a semiconductor device is manufactured by stacking a plurality of semiconductor chips. In particular, a photosensitive adhesive composition capable of continuous pressure bonding, a method for producing a patterned cured film using the same, and an electronic component having the patterned cured film obtained thereby can be provided. The patterned cured film made of the photosensitive adhesive composition of the present invention exhibits excellent crack resistance and adhesion, has good photosensitive properties (sensitivity and resolution), and has sufficient mechanical properties (breaking elongation and Elastic modulus). Since the photosensitive adhesive composition of the present invention can be cured at a low temperature, the electronic component can be prevented from being damaged by heat, and a highly reliable electronic component can be provided with a high yield.

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]
The photosensitive adhesive composition according to the present embodiment contains (A) an alkali-soluble resin having a phenolic hydroxyl group, (B) a compound that generates an acid by light, and (C) a thermal crosslinking agent.

<(A) component: alkali-soluble resin having a phenolic hydroxyl group>
The component (A) is an alkali-soluble resin having a phenolic hydroxyl group (soluble in an aqueous alkali solution). Here, one standard that the component (A) of the present invention is soluble in an alkaline aqueous solution will be described below. A resin solution obtained from the component (A) alone and an arbitrary solvent or the component (A) and the components (B), (C), and (D), which will be described in the following order, is a substrate such as a silicon wafer. A resin film having a thickness of about 5 μm is formed by spin coating. This is immersed in any one of tetramethylammonium hydroxide aqueous solution, metal hydroxide aqueous solution, and organic amine aqueous solution at 20-25 ° C. As a result, when the resin film can be dissolved as a uniform solution, it is determined that the used component (A) is soluble in an alkaline aqueous solution.

  The alkali-soluble resin having a phenolic hydroxyl group as the component (A) has a structural unit represented by the following general formula (3).

［一般式（３）中、Ｒ^９は水素原子又はメチル基を示し、Ｒ^１０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の整数を示し、ｂは１〜３の整数を示す。］
（Ａ）フェノール性水酸基を有するアルカリ可溶性樹脂は一般式（３）で表される構造単位を与えるモノマ等を重合させることで得られる。

[In General Formula (3), R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ 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. ]
(A) The alkali-soluble resin having a phenolic hydroxyl group can be obtained by polymerizing a monomer or the like that gives the structural unit represented by the general formula (3).

In the general formula (3), examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁰ 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, and a nonyl group. Groups and decyl groups. These groups may be linear or branched. Moreover, as a C6-C10 aryl group, a phenyl group and a naphthyl group are mentioned, for example. Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexoxy group, heptoxy group, octoxy group, nonoxy group and decoxy group. These groups may be linear or branched.

  Monomers that give the structural unit represented by the general formula (3) include, for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol, and o-isopropenyl. Phenol etc. are mentioned. These monomers can be used singly or in combination of two or more.

  (A) Although there is no restriction | limiting in particular in the method of obtaining alkali-soluble resin which has a phenolic hydroxyl group, For example, the hydroxyl group of the monomer which gives the structural unit shown by General formula (3) is protected by t-butyl group, an acetyl group, etc. To obtain a polymer by polymerizing the monomer having a hydroxyl group protected, and then subjecting the obtained polymer to a known method (deprotection under an acid catalyst to form a hydroxystyrene structural unit. It is obtained by deprotection by conversion into (1).

  The component (A) may be a polymer or copolymer consisting only of a monomer that gives the structural unit represented by the general formula (3), and a monomer that gives the structural unit represented by the general formula (3) It may be a copolymer with other monomers. When the component (A) is a copolymer, the proportion of the structural unit represented by the general formula (3) in the copolymer is 100 mol of the component (A) from the viewpoint of solubility in an alkaline developer in the exposed area. % Is preferably 10 to 100 mol%, more preferably 20 to 97 mol%, still more preferably 30 to 95 mol%, and particularly preferably 50 to 95 mol%.

  The component (A) preferably further contains an alkali-soluble resin having a structural unit represented by the following general formula (4) from the viewpoint of further improving the dissolution inhibition property of the unexposed portion with respect to the alkaline developer.

［一般式（４）中、Ｒ^１１は水素原子又はメチル基を示し、Ｒ^１２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、ｃは０〜３の整数を示す。］

[In General Formula (4), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² 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. , C represents an integer of 0-3. ]

Alkyl group having 1 to 10 carbon atoms represented by R ^12, the aryl group or an alkoxy group having 1 to 10 carbon atoms having from 6 to 10 carbon atoms, can be exemplified the same as ^{R 10} in formula (3), respectively .

  The alkali-soluble resin having the structural unit represented by the general formula (4) can be obtained by using a monomer that provides the structural unit represented by the general formula (4). Examples of the monomer that gives the structural unit represented by the general formula (4) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, and m-methoxystyrene. And aromatic vinyl compounds such as p-methoxystyrene. These monomers can be used singly or in combination of two or more.

  When an alkali-soluble resin having the structural unit represented by the general formula (4) is included, the structure represented by the general formula (4) from the viewpoint of dissolution inhibition with respect to the alkaline developer in the unexposed area and the mechanical properties of the pattern cured film The unit ratio is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and particularly preferably 5 to 50 mol% with respect to 100 mol% of the component (A).

  The component (A) preferably further contains an alkali-soluble resin having a structural unit represented by the following general formula (5) from the viewpoint of lowering the elastic modulus.

［一般式（５）中、Ｒ^１３は水素原子又はメチル基を示し、Ｒ^１４は炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基を示す。］

[In General Formula (5), R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms. ]

  The alkali-soluble resin having the structural unit represented by the general formula (5) can be obtained by using a monomer that provides the structural unit represented by the general formula (5). Monomers that give the structural unit represented by the general formula (5) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth) Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, hydroxymethyl (meth) acrylate, (meth) Hydroxyethyl acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, (meth) acrylic acid Hydroxyoctyl, hydroxynonyl (meth) acrylate and (Meth) acrylic acid hydroxy decyl. These monomers can be used singly or in combination of two or more.

  When an alkali-soluble resin having the structural unit represented by the general formula (5) is included, the structure represented by the general formula (5) from the viewpoint of dissolution inhibition of the unexposed portion with respect to the alkaline developer and the mechanical properties of the pattern cured film The unit ratio is preferably 1 to 90 mol%, more preferably 3 to 80 mol%, still more preferably 5 to 70 mol%, and particularly preferably 5 to 50 mol% with respect to 100 mol% of the component (A).

  The alkali-soluble resin having a phenolic hydroxyl group as the component (A) is a structural unit represented by the general formula (3) and a general formula from the viewpoint of dissolution inhibition with respect to an alkali developer in an unexposed area and mechanical properties of the pattern cured film. An alkali-soluble resin having a structural unit represented by (4), an alkali-soluble resin having a structural unit represented by general formula (3) and a structural unit represented by general formula (5), general formula (3) ), A structural unit represented by general formula (4), and an alkali-soluble resin having a structural unit represented by general formula (5). From the viewpoint of more manifesting the effects of the present invention, an alkali-soluble resin having a structural unit represented by the general formula (3) and a structural unit represented by the general formula (4) or (5) is more preferable. .

  The molecular weight of the component (A) is preferably 1000 to 500000, more preferably 2000 to 200000, more preferably 2000 to 100000 in terms of weight average molecular weight, considering the balance of solubility in an alkaline aqueous solution, photosensitive properties, and mechanical properties of the cured pattern film. More preferably it is. 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.

<(B) component: Compound that generates acid by light>
The compound which produces | generates an acid with the light which is (B) component is used as a photosensitive agent. The component (B) has a function of generating an acid by light irradiation and increasing the solubility of the light-irradiated portion in the 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. Of these, o-quinonediazide compounds are preferred because of their high sensitivity.

  The o-quinonediazide compound is obtained, for example, by a method in which o-quinonediazidesulfonyl chloride is subjected to a condensation reaction in the presence of a dehydrochlorinating agent with a hydroxyl compound or an amino compound.

  Examples of the o-quinonediazidesulfonyl 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-4- A sulfonyl chloride is mentioned.

  Examples of the hydroxyl compound used in the reaction include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3,4- Trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,2 ′, 3′-pentahydroxybenzophenone, 2,3 , 4,3 ′, 4 ′, 5′-hexahydroxybenzophenone, bis (2,3,4-trihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) propane, 4b, 5,9b, 10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylind [2,1-a] indene, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4 -Hydroxyphenyl) -1-methylethyl} phenyl] 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, pyridine and the like. As the reaction solvent, dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, N-methylpyrrolidone, or the like is used.

  o-quinonediazide sulfonyl chloride and hydroxyl compound and / or amino compound are blended so that the total number of moles of hydroxyl group and amino group is 0.5 to 1 per mole of o-quinonediazide sulfonyl 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.

  The preferable reaction temperature of the above reaction is 0 to 40 ° C., and the preferable reaction time is 1 to 10 hours.

  The content of the component (B) is preferably 3 to 100 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint that the difference in dissolution rate between the exposed part and the unexposed part increases and the sensitivity becomes better. 5-50 mass parts is more preferable, and 5-30 mass parts is further more preferable.

<(C) component: thermal crosslinking material>
(C) The compound which has the alkyl etherified amino group shown to following General formula (1) is used for the heat-crosslinking material of a component.

［一般式（１）中、Ｒ^１〜Ｒ^６は、それぞれ独立に炭素数１〜１０のアルキル基を示す。］

[In the general formula ^(1), R 1 ~R ⁶ represents an alkyl group having 1 to 10 carbon atoms independently. ]

In the general formula (1), examples of the alkyl group having 1 to 10 carbon atoms represented by R ^{1 to} R ⁶ 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 are mentioned. These groups may be linear or branched. Specific examples of the compound having an alkyl etherified amino group represented by the general formula (1) include hexakis (methoxymethyl) melamine and hexakis (butoxymethyl) melamine.
The content of the compound having an alkyl etherified amino group represented by the general formula (1) is such that the difference in dissolution rate between the exposed and unexposed areas is increased, and the sensitivity is improved, and the press bonding property during thermocompression bonding From the viewpoint of the stability of the component (A), 0.1 to 2 parts by mass is preferable, 100 to 0.2 parts by mass is more preferable, and 0.3 to 1.8 parts by mass is preferable with respect to 100 parts by mass of the component. Further preferred.
When the compounding amount of the alkyl etherized compound having an amino group is 0.1 parts by mass or less, developability at the time of pattern formation is deteriorated. On the other hand, if the compounding amount of the alkyl etherified compound having an amino group exceeds 2 parts by mass, the adhesiveness deteriorates during continuous pressure bonding.

  The component (C) thermal crosslinking material may further contain a compound having a structure capable of reacting with the component (A) to form a bridge structure when the pattern resin film is cured by heating. Thereby, the brittleness of the film and the melting of the film can be prevented. These thermal crosslinking agents are 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 the alkali-soluble resin having a phenolic hydroxyl group as 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 weight average molecular weight of such a compound having a phenolic hydroxyl group is preferably 2000 or less, more preferably 94 to 2000 in consideration of the balance of solubility in an alkaline aqueous solution, photosensitive property and mechanical property. 108 to 2000 is more preferable, and 108 to 1500 is particularly preferable.

  As the compound having a phenolic hydroxyl group, conventionally known compounds can be used, but the compound represented by the following general formula (6) is effective in promoting the dissolution of the exposed portion and melting at the time of curing the photosensitive resin film. Since it is excellent in the balance of the effect to prevent, it is preferable.

［一般式（６）中、Ｘは単結合又は２価の有機基を示し、Ｒ^１５、Ｒ^１６、Ｒ^１７及びＲ^１８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０〜３の整数を示す。］

[In General Formula (6), X represents a single bond or a divalent organic group, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom or a monovalent organic group, and s and t each independently represents an integer of 1 to 3, and u and v each independently represents an integer of 0 to 3. ]

In the general formula (6), the compound in which X is a single bond is a biphenol (dihydroxybiphenyl) derivative. Examples of the divalent organic group represented by X include, for example, an alkylene group having 1 to 10 carbon atoms such as a methylene group, an ethylene group, and a propylene group, an alkylidene group having 2 to 10 carbon atoms such as an ethylidene group, and a phenylene group. An arylene group having 6 to 30 carbon atoms such as a group, 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, and an amide bond Is mentioned. Furthermore, as monovalent organic groups represented by R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ , for example, carbon groups such as alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl and propyl groups, and vinyl groups and the like Examples include C2-C30 aryl groups such as alkenyl groups of 2 to 10 and phenyl groups, and groups in which some or all of hydrogen atoms of these hydrocarbon groups are substituted with halogen atoms such as fluorine atoms.
Examples of the compound represented by the general formula (6) include 1,1-bis {3,5-bis (methoxymethyl) -4-hydroxyphenyl} methane (trade name “TMOM-” manufactured by Honshu Chemical Industry Co., Ltd.). pp-BPF ").

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

  Among the components (C) described above, it is preferable to use a compound having a phenolic hydroxyl group or a compound having a hydroxymethylamino group from the viewpoint that the sensitivity and heat resistance can be further improved, and the resolution and elongation of the coating film are also improved. From the point of view, a compound having a hydroxymethylamino group is more preferable, a compound having an alkoxymethylamino group in which all or part of the hydroxymethylamino group is alkyletherified is more preferable, and all of the hydroxymethylamino group is alkyletherified. Particularly preferred are compounds having an alkoxymethylamino group.

You may contain an epoxy resin further as a heat-crosslinking material. A conventionally well-known thing can be used as a compound which has an epoxy resin. Specific examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, glycidyl amine, heterocyclic epoxy resin and polyalkylene glycol diglycidyl. Ether.
Among the epoxy resin components described above, a compound represented by the following general formula (7) is preferable.

[一般式(７)中、Ｒ^１はＣ２〜Ｃ４のアルキル鎖を表す。ｎは１〜９の整数を表す。]
これらのエポキシ樹脂には、不純物イオンであるアルカリ金属イオン、アルカリ土類金属イオン、ハロゲンイオン、特に塩素イオンや加水分解性塩素等を３００ｐｐｍ以下に低減した高純度品を用いることが、エレクトロマイグレーション防止や金属導体回路の腐食防止のために好ましい。
これらのエポキシ樹脂は単独で又は２種類以上を組合せて使用することができる。
また、使用するエポキシ樹脂は、５％質量減少温度が１５０℃以上であることが好ましく、１８０℃以上であることがより好ましく、２００℃以上であることが更に好ましく、２６０℃以上であることが最も好ましい。５％質量減少温度が１５０℃以上であることで、低アウトガス性、高温接着性、耐リフロー性が向上する。
エポキシ樹脂の含有量は、半硬化膜への柔軟性を付与する観点から、（Ａ）成分１００質量部に対して０．５〜５０質量部が好ましく、１〜４０質量部がより好ましく、２〜３０質量部がさらに好ましい。

[In General Formula (7), R ¹ represents a C2-C4 alkyl chain. n represents an integer of 1 to 9. ]
For these epoxy resins, it is necessary to use high-purity products in which alkali metal ions, alkaline earth metal ions, halogen ions, especially chlorine ions and hydrolyzable chlorine, which are impurity ions, are reduced to 300 ppm or less to prevent electromigration. And for preventing corrosion of metal conductor circuits.
These epoxy resins can be used alone or in combination of two or more.
The epoxy resin used preferably has a 5% mass reduction temperature of 150 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 200 ° C. or higher, and 260 ° C. or higher. Most preferred. When the 5% mass reduction temperature is 150 ° C. or higher, low outgassing property, high temperature adhesion property, and reflow resistance are improved.
From the viewpoint of imparting flexibility to the semi-cured film, the content of the epoxy resin is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass with respect to 100 parts by mass of the component (A). -30 mass parts is more preferable.

  Examples of the thermal crosslinking material that may be used in combination with the thermal crosslinking material of component (C) include, in addition to the compounds described above, bis [3,4-bis (hydroxymethyl) phenyl] ether, 1,3,5-tris, for example. Aromatic compounds having a hydroxymethyl group such as (1-hydroxy-1-methylethyl) benzene, bis (4-maleimidophenyl) methane, 2,2-bis [4- (4′-maleimidophenoxy) phenyl] propane, etc. A compound having a maleimide group, a compound having a norbornene skeleton, a polyfunctional acrylate compound, a compound having an oxetanyl group, a compound having a vinyl group, and a blocked isocyanate compound can also be used.

As a process using the photosensitive adhesive composition, 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 materials having different reaction temperatures. It is known that the compound having an alkyl etherified amino group represented by the general formula (1) of the component (C) proceeds at a temperature lower than the pressure bonding temperature of 80 to 150 ° C. Moreover, it is known that an epoxy resin will react at 150-230 degreeC.
By using the above-mentioned thermal crosslinking material in combination, semi-curing can be performed once at 80 to 150 ° C. 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, adhesive strength with a to-be-adhered body can be strengthened by advancing hardening at 150-200 degreeC after pressure bonding.

<(D) component: Silane compound>
The photosensitive adhesive composition according to the present embodiment contains a silane compound having an epoxy group represented by the general formula (2) as the component (D) from the viewpoint of further improving the adhesion to the substrate. It may be.

In the general formula (2), R ⁷ represents a divalent organic group, and the R ⁸ group represents a monovalent organic group. A plurality of R ⁸ in the same molecule may be the same or different.

In general formula (2), from the viewpoint of improving sensitivity and resolution, R ⁷ is preferably a linear alkylene group represented by — (CH ₂ ) _n — (n is an integer of 1 to 6). R ⁸ is preferably an alkoxy group, an alkoxyalkyl group, or an alkyl group from the viewpoint of improving sensitivity and resolution. Among these, R ⁸ is particularly preferably an alkoxy group such as a methoxy group and an ethoxy group from the viewpoints of being inexpensive and easily available and improving the adhesion to the substrate. Examples of such compounds include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane.

  The photosensitive adhesive composition according to the present embodiment may further contain a silane compound different from the silane compound as the component (D) represented by the general formula (2). Examples of such silane compounds include ureidopropyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, urea propyltriethoxysilane, methylphenylsilanediol, ethylphenylsilanediol, and n-propylphenyl. Silanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, 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 (ethyl) Dihydroxysilyl) benzene, 1,4-bis (propyldihydroxysilyl) benzene, 1,4-bis (butyldihydride) Loxysilyl) benzene, 1,4-bis (dimethylhydroxysilyl) benzene, 1,4-bis (diethylhydroxysilyl) benzene, 1,4-bis (dipropylhydroxysilyl) benzene, 1,4-bis (dibutylhydroxysilyl) ) Benzene and the like. These silane compounds are used alone or in combination of two or more.

  From the viewpoint of adhesiveness to wiring and storage stability of the photosensitive adhesive composition, the total amount of the silane compound other than the (D) component and the (D) component is 0.001 with respect to 100 parts by mass of the (A) component. It is preferable that it is -20 mass parts, 0.005-15 mass parts is more preferable, and 0.01-10 mass parts is further more preferable.

<(E) component>
The acrylic resin as the component (E) has a structural unit represented by the following general formula (8).

［一般式（８）中、Ｒ^１９は水素原子又はメチル基を示し、Ｒ^２０は炭素数２〜２０のヒドロキシアルキル基を示す。］
本実施形態の感光性接着剤組成物は、一般式（８）で表される構造単位を有する（Ｅ）成分を含有することにより、感光性接着剤の白濁を充分に抑え、パターン硬化膜のヘーズ値を低くすることができる。また、（Ｅ）成分を含有することにより、感光特性及び熱衝撃性（高温放置後及び冷熱衝撃試験後での機械特性の変化率が小さいこと）をより向上することができる。（Ｅ）成分は、１種のアクリル樹脂のみからなるものであってもよく、２種以上のアクリル樹脂を含むものであってもよい。

[In General Formula (8), R ¹⁹ represents a hydrogen atom or a methyl group, and R ²⁰ represents a hydroxyalkyl group having 2 to ²⁰ carbon atoms. ]
The photosensitive adhesive composition of the present embodiment contains the component (E) having the structural unit represented by the general formula (8), thereby sufficiently suppressing the white turbidity of the photosensitive adhesive, The haze value can be lowered. Further, by containing the component (E), it is possible to further improve the photosensitive characteristics and thermal shock properties (the rate of change in mechanical characteristics after standing at high temperature and after the thermal shock test is small). (E) A component may consist only of 1 type of acrylic resins, and may contain 2 or more types of acrylic resins.

  Since the component (E) contains the structural unit represented by the general formula (8), the interaction between the component (E) and the component (A) is improved and the compatibility is improved. Adhesion to the substrate, mechanical properties and thermal shock properties can be further improved.

In general formula (8), R ⁴ is preferably a hydroxyalkyl group having 2 to 15 carbon atoms, and a hydroxyalkyl group having 2 to 10 carbon atoms from the viewpoint that the compatibility with the component (A) and thermal shock resistance can be further improved. Are more preferable, and a hydroxyalkyl group having 2 to 8 carbon atoms is particularly preferable.
Examples of the hydroxyalkyl group having 2 to 20 carbon atoms represented by R ⁴ include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, a hydroxyhexyl group, a hydroxyheptyl group, a hydroxyoctyl group, and a hydroxynonyl group. , Hydroxydecyl group, hydroxyundecyl group, hydroxydodecyl group (sometimes referred to as hydroxylauryl group), hydroxytridecyl group, hydroxytetradecyl group, hydroxypentadecyl group, hydroxyhexadecyl group, hydroxyheptadecyl group, hydroxy Examples include octadecyl group, hydroxynonadecyl group and hydroxyeicosyl group. These groups may be linear or branched.

As a monomer which gives the acrylic resin which has a structural unit represented by General formula (8), (meth) acrylic-acid hydroxyalkyl is mentioned, for example.
Examples of such a hydroxyalkyl (meth) acrylate include compounds represented by the following general formula (9).

^{_{CH 2 = C (R 19)}} -COOR 20 ... (9)
[In General Formula (9), R ¹⁹ represents a hydrogen atom or a methyl group, and R ²⁰ represents a hydroxyalkyl group having 2 to ²⁰ carbon atoms. ]
In addition, it is desirable to add the acrylic resin which has a structural unit represented by General formula (8) as a polymer from a viewpoint which can express the effect of this invention more highly.

  Examples of the monomer represented by the general formula (9) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, (meth ) Hydroxyhexyl acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyundecyl (meth) acrylate, (meth) Hydroxy dodecyl acrylate (sometimes referred to as hydroxy lauryl (meth) acrylate), hydroxy tridecyl (meth) acrylate, hydroxy tetradecyl (meth) acrylate, hydroxy pentadecyl (meth) acrylate, (meth) acryl Acid hydro Shihekisadeshiru, (meth) acrylic acid hydroxy heptadecyl, (meth) acrylic acid hydroxy octadecyl, and (meth) acrylic acid hydroxy nonadecyl and (meth) acrylic acid hydroxy eicosyl. These monomers are used alone or in combination of two or more. Among these, from the viewpoint of further improving the compatibility with the component (A) and the elongation at break, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylic Hydroxypentyl acid, hydroxyhexyl (meth) acrylate, hydroxyheptyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxynonyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxy (meth) acrylate It is preferable to use undecyl or hydroxydodecyl (meth) acrylate.

  The component (E) may be an acrylic resin composed only of the structural unit represented by the general formula (8), or an acrylic resin having a structural unit other than the structural unit represented by the general formula (8). Also good. When the acrylic resin has a structural unit other than the structural unit represented by the general formula (8), the proportion of the structural unit represented by the general formula (8) in the acrylic resin is based on the total amount of the component (E). The content is preferably 0.1 to 30 mol%, more preferably 0.3 to 20 mol%, and still more preferably 0.5 to 10 mol%. When the compositional ratio of the structural unit represented by the general formula (8) is 0.1 to 30 mol%, the compatibility with the component (A) and the thermal shock resistance of the pattern cured film can be further improved. it can.

  The component (E) is preferably an acrylic resin having a structural unit represented by the following general formula (10).

［一般式（１０）中、Ｒ^２１は水素原子又はメチル基を示し、Ｒ^２２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。］
（Ｅ）成分が一般式（１０）で表される構造単位を有することで、未露光部の現像液に対する溶解阻害性をより向上できる。

[In General Formula (10), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a monovalent organic group having a primary, secondary, or tertiary amino group. ]
When the component (E) has the structural unit represented by the general formula (10), it is possible to further improve the dissolution inhibition property of the unexposed portion with respect to the developer.

Monomers that give an acrylic resin having a structural unit represented by the general formula (10) include, for example, 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-ethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, piperidin-4-yl (meth) acrylate, 1-methylpiperidin-4-yl (meth) acrylate, 2,2, 6,6-tetramethylpiperi 4-yl (meth) acrylate, 1,2,2,6,6-pentamethylpiperidin-4-yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate and 2- (piperidine- 4-yl) ethyl (meth) acrylate. These monomers are used alone or in combination of two or more. Among these, from the viewpoint of further improving the adhesion of the patterned cured film to the substrate, mechanical properties, and thermal shock resistance, in the general formula (10), R ²² is a monovalent represented by the following general formula (11). An organic group is preferred.

［一般式（１１）中、Ｙは炭素数１〜５のアルキレン基を示し、Ｒ^２３〜Ｒ^２７は各々独立に水素原子又は炭素数１〜２０のアルキル基を示し、ｎは０〜１０の整数を示す。］

[In General Formula (11), Y represents an alkylene group having 1 to 5 carbon atoms, R ^{23 to} R ²⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and n represents 0 to 10 carbon atoms. Indicates an integer. ]

In the general formula (10), examples of the polymerizable monomer that gives a structural unit in which R ²² is a monovalent organic group represented by the general formula (11) 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-pentamethylpiperidine-4 -Yl (meth) acrylate, (piperidin-4-yl) methyl (meth) acrylate and 2- (piperidin-4-yl) ethyl (meth) acrylate. 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. (Each is made by Hitachi Chemical Co., Ltd.) and is preferable because it is commercially available.

  (E) When the acrylic resin has the structural unit represented by the general formula (10), the proportion of the structural unit represented by the general formula (10) is the compatibility with the component (A) and the solubility in the developer. From this point, it is preferably 0.3 to 10 mol%, more preferably 0.4 to 6 mol%, and more preferably 0.5 to 5 mol%, based on the total amount of component (E). More preferably.

  The component (E) is preferably an acrylic resin having a structural unit represented by the following general formula (12).

［一般式（１２）中、Ｒ^２８は水素原子又はメチル基を示し、Ｒ^２９は炭素数４〜２０のアルキル基を示す。］
（Ｅ）成分が一般式（１２）で表される構造単位を有することで、未露光部の現像液に対する溶解阻害性をより向上できる。
一般式（１２）中、Ｒ^２９で示される炭素数４〜２０のアルキル基としては、例えば、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基（ラウリル基という場合もある。）、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基及びエイコシル基が挙げられる。これらの基は直鎖状であっても分岐鎖状であってもよい。

[In General Formula (12), R ²⁸ represents a hydrogen atom or a methyl group, and R ²⁹ represents an alkyl group having 4 to 20 carbon atoms. ]
When the component (E) has the structural unit represented by the general formula (12), it is possible to further improve the dissolution inhibition property of the unexposed portion with respect to the developer.
In the general formula (12), examples of the alkyl group having 4 to 20 carbon atoms represented by R ²⁹ include butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group. Group (sometimes referred to as lauryl group), tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and eicosyl group. These groups may be linear or branched.

In general formula (12), R ²⁹ is preferably an alkyl group having 4 to 16 carbon atoms, more preferably an alkyl group having 4 to 12 carbon atoms, from the viewpoint that sensitivity, resolution, and thermal shock can be further improved. Preferably, it is a C4 alkyl group (n-butyl group).

Examples of the monomer that gives the structural unit represented by the general formula (12) include alkyl (meth) acrylate. As alkyl (meth) acrylate, the compound represented by following General formula (13) is mentioned, for example.

^{_{CH 2 = C (R 28)}} -COOR 29 ... (13)
[In General Formula (13), R ²⁸ represents a hydrogen atom or a methyl group, and R ²⁹ represents an alkyl group having 4 to 20 carbon atoms. ]

  Examples of the monomer represented by the general formula (13) include, for example, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, Nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate (sometimes called lauryl (meth) acrylate), tridecyl (meth) acrylate, (meta And tetradecyl acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate and eicosyl (meth) acrylate. These polymerizable monomers are used alone or in combination of two or more. Among these, from the viewpoint of further improving elongation at break and lowering the elastic modulus, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, (meth) It is preferable to use octyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate or dodecyl (meth) acrylate (also referred to as lauryl (meth) acrylate).

  (E) When an acrylic resin has a structural unit represented by General formula (12), the ratio of the structural unit represented by General formula (12) is 50-93 mol with respect to the total amount of (E) component. %, More preferably 55 to 85 mol%, and still more preferably 60 to 80 mol%. When the proportion of the structural unit represented by the general formula (12) is 50 to 93 mol%, the thermal shock resistance of the pattern cured film can be further improved.

  The component (E) is preferably an acrylic resin having a structural unit represented by the following general formula (14).

［一般式（１４）中、Ｒ^３０は水素原子又はメチル基を示す。］
（Ｅ）成分が一般式（１４）で表される構造単位を有することで、感度をより向上することができる。

[In General Formula (14), R ³⁰ represents a hydrogen atom or a methyl group. ]
(E) Since a component has a structural unit represented by General formula (14), a sensitivity can be improved more.

  Examples of the monomer that gives the structural unit represented by the general formula (14) include acrylic acid and methacrylic acid.

  (E) When an acrylic resin has a structural unit represented by General formula (14), the ratio of the structural unit represented by General formula (14) is 5-35 mol with respect to the total amount of (E) component. %, More preferably 10 to 30 mol%, still more preferably 15 to 25 mol%. When the compositional ratio of the structural unit represented by the general formula (14) is 5 to 35 mol%, compatibility with the component (A) and developability can be further improved.

  The component (E) includes, for example, a monomer that gives the structural unit represented by the general formula (8) and a structure represented by the general formulas (9), (12), and (14) that are added as necessary. It is obtained by blending a monomer that gives a unit, stirring in a solvent such as ethyl lactate, toluene, isopropanol, and heating as necessary.

  The monomer used for the synthesis of the (E) acrylic resin may further contain a monomer other than the monomer that gives the structural unit represented by the general formulas (8), (9), (12), and (14). Good.

  Examples of such monomers include benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, acrylonitrile, esters of vinyl alcohol such as vinyl-n-butyl ether, tetrahydrofurfuryl (meth) acrylate, Glycidyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, α-bromo (meth) acrylic acid, α-chloro ( Maleic acid monoesters such as (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, Fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, chloro Tonic acid and propiolic acid are mentioned. These monomers are used alone or in combination of two or more.

  (E) 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 further more preferable that it is 5000-50000, It is especially 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 100,000 or less, the compatibility with the component (A) and the developability can be further improved. 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.

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

<Other ingredients>
The photosensitive adhesive composition according to this embodiment can contain other components such as a thermal acid generator, an elastomer, a solvent, a dissolution accelerator, a dissolution inhibitor, a surfactant, or a leveling agent as necessary. .

<Other components (F): Thermal acid generator>
The photosensitive adhesive composition may contain (F) a thermal acid generator. (F) The thermal acid generator is a compound that generates an acid by heat, and can further suppress the melt of the pattern. This makes it possible to generate an acid when the photosensitive adhesive composition film after development is heated. The component (A) (alkali-soluble resin having a phenolic hydroxyl group) and the component (C) (thermal crosslinking agent) ), That is, the thermal crosslinking reaction starts at a lower temperature, so that the melt of the pattern is further suppressed. Moreover, since many thermal acid generators can generate an acid even when irradiated with light, the use of such a thermal acid generator can increase the solubility of an exposed portion in an alkaline aqueous solution. 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. However, the thermal acid generator said here is a compound different from the said (B) component (compound which produces | generates an acid by light).

  It is preferable that the compound which produces | generates an acid with such a heat | fever produces | generates an acid by heating to the temperature of 100-200 degreeC, for example. Specific examples of the compound that generates an acid by heat include a strong acid and a base such as an onium salt that is different from the compound that generates an acid by the light of the component (B) and has a function of generating an acid by heat. And salts formed from imide sulfonate.

Examples of such onium salts include diaryliodonium salts such as aryldiazonium salts and diphenyliodonium salts; di (alkylaryl) iodonium salts such as di (t-butylphenyl) iodonium salts; and trimethylsulfonium salts. Examples include trialkylsulfonium salts; dialkylmonoarylsulfonium salts such as dimethylphenylsulfonium salts; diarylmonoalkyliodonium salts such as diphenylmethylsulfonium salts; and triarylsulfonium salts. 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 Preferred examples include dimethylphenylsulfonium salt and diphenylmethylsulfonium salt of toluenesulfonic acid.
(F) As for content in the case of containing a thermal acid generator, 0.1-30 mass parts is preferable with respect to 100 mass parts of total amounts of (A) component and (B) component, and 0.2-20 A mass part is more preferable and 0.3-10 mass parts is still more preferable.

<Other components (G): Elastomer>
The photosensitive adhesive composition may further contain (G) an elastomer. Thereby, the obtained pattern cured film becomes further excellent in terms of flexibility, and the mechanical properties and thermal shock resistance of the pattern cured film can be further improved. A conventionally known elastomer can be used as the elastomer, but the glass transition temperature (Tg) of the polymer constituting the elastomer is preferably 20 ° C. or lower.

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

<Other components (H): Solvent>
The photosensitive adhesive composition may contain (H) a solvent from the viewpoint that it can be applied onto a substrate and a resin film having a uniform thickness can be formed. Specific examples of the solvent include γ-butyrolactone, 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, hexamethylphosphorylamide, tetramethylene sulfone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene Examples include glycol monobutyl ether and dipropylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more. (H) Although content in the case of containing a component is not specifically limited, It is preferable to adjust so that the ratio of the solvent in a photosensitive adhesive may be 20-90 mass%.

<Other components (I): dissolution promoter>
The photosensitive adhesive composition may contain (I) a dissolution accelerator. (I) By containing a dissolution accelerator, it is possible to increase the dissolution rate of the exposed area when the pattern resin film is developed with an alkaline aqueous solution, and to improve sensitivity and resolution. 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 containing such a dissolution accelerator can be determined by the dissolution rate of the pattern resin film in the alkaline aqueous solution. For example, 0.01 to 30 parts per 100 parts by mass of the component (A). It is preferable to set it as a mass part.

<Other components (J): Dissolution inhibitor>
The photosensitive adhesive composition may contain (J) a dissolution inhibitor. (J) 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, diphenyliodonium iodide and the like. In the case of containing a dissolution inhibitor, the content is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A), in terms of sensitivity and the allowable range of development time, and 0.01 to 15 Mass parts are more preferable, and 0.05 to 10 parts by mass are even more preferable.

<Other components (K): Surfactant or leveling agent>
The photosensitive adhesive composition may contain (K) a surfactant or a leveling agent. When the photosensitive adhesive composition contains the component (K), coating properties such as striation (film thickness unevenness) can be prevented or developability can be improved. Examples of such a surfactant or leveling agent include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octylphenol ether. Commercially available products include Megafax F171, F173, R-08 (manufactured by DIC Corporation, trade name), Florard FC430, FC431 (Sumitomo 3M Corporation, trade name), organosiloxane polymers KP341, KBM303, KBM803 (Shin-Etsu Chemical Co., Ltd.) Product name).
(K) When containing a component, 0.001-5 mass parts is preferable with respect to 100 mass parts of (A) component, and its content is more preferable 0.01-3 mass parts.

  The photosensitive adhesive composition can be developed using an alkaline aqueous solution such as tetramethylammonium hydroxide (TMAH). Furthermore, by using the above-mentioned photosensitive adhesive composition, 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 of this invention has a favorable photosensitive characteristic (sensitivity and resolution), and has sufficient mechanical characteristics (breaking elongation and elastic modulus).

<Method for Manufacturing Semiconductor Device>
Next, a manufacturing process of a semiconductor device will be described as an example of a method for manufacturing a patterned cured film of the present invention. FIG. 1 is a schematic cross-sectional view showing an embodiment of a semiconductor device having a photosensitive adhesive layer.

The manufacturing method according to this embodiment mainly includes the following steps.
The method for producing a cured pattern film of the present invention comprises a step of applying a photosensitive adhesive composition onto a substrate using the photosensitive adhesive composition of the present invention and drying to form a photosensitive adhesive composition film. The step of exposing the photosensitive adhesive composition, the step of developing the photosensitive adhesive composition film after exposure with an alkaline aqueous solution to form a pattern resin film, and the pattern resin film of 70 to 200 The substrate and the adherend are processed by reactive ion etching and plasma ashing after being heated at 1 ° C. for 1 to 60 minutes, and the adherend is thermocompression bonded to the pattern resin film at 80 to 200 ° C. for 1 to 180 seconds. Adhering to each other.

In a method for manufacturing a semiconductor device,
Step 1: A photosensitive adhesive composition is applied to the circuit surface of a semiconductor wafer.
Process 2: Exposure is performed on the adhesive layer made of the applied photosensitive adhesive composition. Examples of the radiation used for exposure include ultraviolet rays such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a g-line stepper, and an i-line stepper, an electron beam, and laser light. Although exposure amount is appropriately selected depending on the light source or a resin film thickness to be used, for example, in the case of ultraviolet radiation from a high pressure mercury lamp, a 500 mJ / cm ² about the resin thickness 5 to 10 [mu] m.
Process 3: A desired pattern is formed by developing the exposed adhesive layer using an alkaline developer or the like to dissolve and remove the exposed portion of the photosensitive adhesive layer.
Step 4: The semiconductor wafer on which the adhesive layer is formed is heated to remove the remaining solvent, and half-cured.
Step 5: After removing the SiN film at the opening of the photosensitive adhesive layer by reactive ion etching, oxygen plasma ashing is performed to clean the photosensitive adhesive layer.
Step 6: Wafer thinning and chip separation Step 7: Stacking chips.
Step 8: Curing of Adhesive Layer Hereinafter, each step will be described.

Step 1: Application 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. The application by spin coating is preferably performed at a rotational speed of 500 to 5000 rpm (rotation / minute) in order to prevent the wafer from waviness and the rising of the edge portion. From the same viewpoint, the rotational speed is more preferably 600 to 4000 rpm (rotation / minute).

  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, N, N-dimethylformamide (DMF), N-methyl-2- A high boiling point solvent such as pyrrolidone (NMP) 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 in an atmosphere such as a vacuum, nitrogen, or air. 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: Development The exposed adhesive layer is developed, and the above-mentioned dicing line part and the adhesive layer in the part (bonding pad part) for electrical connection are removed, so that the adhesive is separated into pieces. A layer (adhesive pattern) is formed. Development is performed using an alkali developer or an organic solvent. Examples of the alkali developer include alkali aqueous solutions such as alkali metal carbonates, alkali metal hydroxides, and tetraammonium hydroxide (tetramethylammonium hydride). Examples of the organic solvent include DMF, NMP and the like. 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: Removal of residual solvent and 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 material 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, it is possible to suppress gas generation during the press-bonding and curing described later, and to have good press-bonding properties. 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 material to partially proceed by this heating.
Step 5: Etching and Ashing Process Etching is performed using the pattern of the adhesive layer as a mask. 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 carbon tetrafluoride 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: Stacking and Crimping Chips An adherend (a semiconductor element mounting support member, a chip) is pressure-bonded to the adhesive layer surface of the chip (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. for 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 less, and more preferably 50 gf or more. When the tack strength is 80 gf or more, collet adhesion occurs during thermocompression bonding.

Process 8: Curing of adhesive layer After pressure-bonding an 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, semiconductor chips 2 separated into support members (semiconductor element mounting support members) 13 for semiconductor devices are stacked via an adhesive member 30, and further semiconductors are formed on the semiconductor chips 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 a sealing material 15 to obtain a semiconductor device.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
<Preparation of photosensitive adhesive composition>
The following A1 and A2 were prepared as the component (A) (alkali-soluble resin having a phenolic hydroxyl group).
A1: A total of 100 parts by mass of pt-butoxystyrene and styrene in a molar ratio of 85:15 was prepared, and these were dissolved in 150 parts by mass of propylene glycol monomethyl ether, and the reaction temperature was 70 ° C. in a nitrogen atmosphere. The mixture was stirred for 10 hours with 4 parts by mass of azobisisobutyronitrile at a stirring speed of about 160 rpm (rotation / min) to carry out polymerization. Thereafter, sulfuric acid was added to the reaction solution, and the reaction temperature was kept at 90 ° C. for reaction for 10 hours, and pt-butoxystyrene was deprotected and converted to hydroxystyrene. Ethyl acetate was added to the obtained copolymer, washing with water was repeated 5 times, the ethyl acetate phase was separated, the solvent was removed, and p-hydroxystyrene / styrene copolymer A1 was obtained. The weight average molecular weight (Mw) in terms of polystyrene of this copolymer A1 was 10,000. As a result of ¹³ C-NMR analysis, the copolymerization molar ratio of p-hydroxystyrene and styrene was 85:15.
A2: Cresol novolak resin (cresol / formaldehyde novolak resin, m-cresol / p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 13,000, manufactured by Asahi Organic Materials Co., Ltd., trade name “EP4020G”)
(B) 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane as a component (a compound that generates an acid by light) 1-naphthoquinone-2-diazide-5-sulfonic acid ester (esterification rate: about 90%, manufactured by AZ Electronic Materials, trade name “TPPA528”) was prepared.

As the component (C) (thermal crosslinking agent), the following thermal crosslinking material was prepared.
C1: Hexakis (methoxymethyl) melamine (manufactured by Sanwa Chemical Co., Ltd., trade name “Nicarac MW-30HM”) was prepared.
C2: Polyethylene glycol # 400 diglycidyl ether (manufactured by Kyoeisha Chemical Co., Ltd., trade name “Epolite 400E”)
C3: Product name manufactured by Nippon Steel Chemical Co., Ltd. (“ZX-1542, high-purity aliphatic polyglycidyl ether”)
C4: 1,3,5-tris (4,5-epoxypentyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione (manufactured by Nissan Chemical Industries, Ltd., product) Name “TEPIC-VL”)
C5: Novolac type epoxy resin (trade name “EP1032-H60” manufactured by Mitsubishi Chemical Corporation)

  As the component (D) (silane compound represented by the general formula (2)), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-403”) was prepared.

As the component (E) (acrylic resin), an acrylic resin as the component (E) was prepared by the method of Synthesis Example 1 below.
Synthesis Example 1 Synthesis of Acrylic Resin E 75 g of toluene and 75 g of isopropanol (IPA) were weighed into a 500 ml three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, and butyl acrylate weighed separately there. (BA) 85 g, lauryl acrylate (DDA) 24 g, acrylic acid (AA) 14 g, and 1,2,2,6,6-pentamethylpiperidin-4-yl methacrylate (trade name: FA-711MM, Hitachi Chemical Co., Ltd.) 7.9 g polymerizable monomer and 0.13 g azobisisobutyronitrile (AIBN) were added. While stirring at room temperature (25 ° C.) at a stirring speed of about 270 rpm (rotation / min), nitrogen gas was allowed to flow 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. An acrylic resin E was obtained by carrying out a polymerization reaction while maintaining the same temperature for 14 hours. The polymerization rate was 98%. It was the weight average molecular weight (MW) of acrylic resin E calculated | required by standard polystyrene conversion of GPC method = 36,000.

  (H) Ethyl lactate was prepared as a component (solvent).

(Examples 1-5, Comparative Examples 1-2)
(A)-(H) component was mix | blended in the predetermined ratio shown in Table 1. The obtained solution was pressure filtered using a 0.5 μm pore tetrafluoroethylene filter to prepare solutions of the photosensitive adhesives of Examples 1 to 5 and Comparative Examples 1 and 2.

<Evaluation of thermocompression bonding>
The photosensitive adhesive composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes, and a resin film having a thickness of about 12 to 14 μm. After forming, a silicon wafer with a photosensitive adhesive layer was obtained by heating on a hot plate at 150 ° C. for 10 minutes. A dicing sample (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 (25 ° C.) 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 full auto dicer DFD-6361 (made by DISCO Corporation). Cutting is a single-cut method that completes processing with one blade, a disco dicing blade NBC-ZH104F-SE 27HEDD is used for the blade, the blade rotation speed is 45000 rpm (rotation / min), and the cutting speed is 20 mm / s. I went. 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 Hitachi Chemical Techno Service Co., Ltd.), the adhesive layer of the silicon wafer with the adhesive layer diced on the silicon chip of 10 mm × 10 mm × 400 μm (thickness) is placed on the silicon chip side. Lamination was carried out, and pressure bonding was performed under conditions of 150 ° C., 1 s, 100N. Then, the shear adhesive force measurement at room temperature was performed with a shear adhesive force measuring device DAGE-4000 (manufactured by Daisy Japan Co., Ltd.). “○” indicates a value of 1.0 MPa or more, and “×” indicates no value. The thermocompression bonding property was evaluated. The results are shown in Table 1.

<Evaluation of void>
The photosensitive adhesive composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes, and a resin film having a thickness of about 12 to 14 μm. After forming, a silicon wafer with a photosensitive adhesive layer was obtained by heating on a hot plate at 150 ° C. for 10 minutes. A dicing sample (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 (25 ° C.) 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 full auto dicer DFD-6361 (made by DISCO Corporation). Cutting is a single cut method that completes processing with one blade, a disco dicing blade NBC-ZH104F-SE 27HEDD is used for the blade, the blade rotation speed is 45000 rpm (rotation / min), and the cutting speed is 20 mm / s. I went. 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 10.0 mm × 10.0 mm. Next, using a thermocompression bonding machine (manufactured by Hitachi Chemical Techno Service Co., Ltd.), a glass chip of 5 mm × 5 mm × 0.5 mm (thickness) is laminated on the adhesive layer of the diced silicon wafer with an adhesive layer, and 150 The pressure bonding was performed under the conditions of 1 ° C. and 100N. Then, the adhesive layer is observed from the glass chip surface using an optical microscope, and “○” indicates that no void is observed on the glass chip surface-adhesive layer, and “×” indicates that the void is observed. Voids were evaluated. The results are shown in Table 1.

<Evaluation of photosensitive characteristics (sensitivity and resolution)>
The photosensitive adhesive solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were 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. did. 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.
The sensitivity was evaluated with the following exposure amount.
“◯”: 10 to 500 (mJ / cm ² )
“Δ”: 500 to 1000 (mJ / cm ² )
“×”: 1000 (mJ / cm ² ) or more

<Evaluation of elongation at break>
The photosensitive adhesive solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were 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. did. 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 (tetramethylammonium hydroxide) 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. The results are shown in Table 1.

(Evaluation of stage neglectability)
The photosensitive adhesive composition solutions obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were spin-coated on a silicon substrate, heated at 120 ° C. for 3 minutes, and a resin film having a thickness of about 12 to 14 μm. After forming the film, heating was performed at 150 ° C. for 10 minutes on a hot plate to obtain a photosensitive adhesive composition film. 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 full auto dicer DFD-6361 (made by DISCO Corporation). Cutting is a single cut method that completes processing with one blade, a disco dicing blade NBC-ZH104F-SE 27HEDD is used for the blade, the blade rotation speed is 45000 rpm (rotation / min), and the cutting speed is 20 mm / s. I went. 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 150 ° C. for 60 minutes, a silicon chip of 10 mm × 10 mm × 400 μm (thickness) is used by using a thermocompression bonding machine (manufactured by Hitachi Chemical Techno Service Co., Ltd.). 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 conditions of 150 ° C., 1 s, 10N. Then, the shear adhesive force measurement at room temperature was performed with a shear adhesive force measuring device DAGE-4000 (manufactured by Daisy Japan Co., Ltd.). “○” indicates a value of 1.0 MPa or more, and “×” indicates no value. ".

(Tack strength at 150 ° C. of the surface of the photosensitive adhesive composition layer)
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 strength (adhesive strength) at a predetermined temperature was measured, and this was used as the tack strength (tack strength) on the surface of the photosensitive adhesive layer. The tack strength was evaluated as follows.
“O”: 0 to 20 kgf
“△”: 20-80 kgf
“×”: 80 kgf or more

  Examples 1 to 5 have photosensitive characteristics, and have excellent thermocompression bonding properties and die shear strength. When the photosensitive adhesives of Examples 1 to 5 were used, the photosensitive characteristics and mechanical characteristics were also good. On the other hand, when the non-photosensitive resin was used in the same manner as in the examples, it could not be continuously crimped because it had no photosensitivity and high tack strength. In the case where the compound having an alkyl etherified amino group is not used as the component (C) of Comparative Example 2, the sensitivity, resolution, elongation at break, and tack strength are inferior. Comparative Example 1 is (A) an alkali-soluble compound having a phenolic hydroxyl group. The resin 65 (100 parts by mass) contains 5 (7.7 parts by mass) of C-1, which is outside the range of claim 1 with 0.1 to 2 parts by mass, and is inferior in thermocompression bonding.

  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 An adhesive pattern, a semiconductor wafer with an adhesive layer, and a semiconductor device obtained by using the same can be provided. Furthermore, since the photosensitive adhesive of the present invention can be cured at a low temperature, it can prevent damage to the electronic components due to heat, and can provide highly reliable electronic components with a high yield. The electronic component which has the pattern cured film which consists of a photosensitive adhesive 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 having a phenolic hydroxyl group;
(B) a compound that generates an acid by light;
(C) is a photosensitive adhesive composition containing a thermal crosslinking material,
The compound having an alkyl etherified amino group represented by the following general formula (1) as the thermal crosslinking material (C) is 0.1 to 2 parts by mass with respect to 100 parts by mass of the alkali-soluble resin having a phenolic hydroxyl group (A). A photosensitive adhesive composition containing at least

[In the general formula ^(1), R 1 ~R ⁶ represents an alkyl group having 1 to 10 carbon atoms independently. ]   The photosensitive adhesive composition according to claim 1, wherein (B) the compound that generates an acid by light is an o-quinonediazide compound. Furthermore, the photosensitive adhesive composition of Claim 1 or Claim 2 containing the (D) silane compound represented by following General formula (2).

[In General Formula (2), R ⁷ represents a divalent organic group, R ⁸ represents a monovalent organic group, and a plurality of R ⁸ in the same molecule may be the same or different. ]   Furthermore, (E) The photosensitive adhesive composition as described in any one of Claims 1-3 containing an acrylic resin. Applying and drying the photosensitive adhesive composition according to any one of claims 1 to 4 on a substrate to form a photosensitive adhesive composition film;
Exposing the photosensitive adhesive composition film;
Developing the photosensitive adhesive composition film after exposure with an aqueous alkaline solution to form a patterned resin film;
The pattern resin film is heated at 70 to 200 ° C. for 1 to 60 minutes and then processed by reactive ion etching and plasma ashing, and the adherend is thermocompression bonded to the pattern resin film at 80 to 200 ° C. for 1 to 180 seconds. A step of adhering the substrate and the adherend,
A method for producing a patterned cured film.   The electronic component which has a pattern cured film obtained by the manufacturing method of the pattern cured film of Claim 5.

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