JP2009251451A - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition and a photosensitive element which can ensure adequate developability and perform image formation using a thick film with good resolution. <P>SOLUTION: The photosensitive resin composition comprises (A) a polyamic acid having constitutional units represented by formulae (1)-(3), (B) a photopolymerizable compound, and (C) a photopolymerization initiator, wherein Ar<SP>1</SP>represents a tetracarboxylic acid dianhydride residue; Ar<SP>2</SP>and Ar<SP>3</SP>each independently represent a diamine residue, provided that at least one of Ar<SP>1</SP>and Ar<SP>2</SP>has a 5-20C alkylene group in a main chain; and R<SP>1</SP>represents an ethylenically unsaturated group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a photosensitive element.

  Conventionally, polyimide resins and polybenzoxazole resins having excellent heat resistance and excellent electrical characteristics and mechanical characteristics have been used for surface protection films and interlayer insulating films of semiconductor elements.

  Also, in recent years, miniaturization has progressed along with higher performance and higher density of electronic equipment, and heat-resistant insulating resins used for electronic parts and wiring boards are easily processed at a low cost and are inexpensive. There is a demand for imparting photosensitivity capable of forming a pattern using. Examples of such a material include a photosensitive solder resist used for wiring board applications and a photosensitive build-up material used for a photo via method. As the photosensitive resin composition, an alkali developing type composition that can be developed with a dilute alkaline aqueous solution such as an aqueous sodium carbonate solution has become mainstream from the viewpoints of conservation of the working environment and global environment. As such a photosensitive resin composition, for example, the photosensitive resin compositions described in Patent Documents 1 and 2 are known.

  On the other hand, new package applications that have been developed in recent years require lower dielectric constants and thicker interlayer insulation films to solve wiring delays, and development of polyimide-based photosensitive resin materials that can form thick films It is desired. However, in the case of the conventional photosensitive resin composition containing the non-photosensitive polyamic acid and the photopolymerizable compound, the non-photosensitive polyamic acid oozes out from the pattern edge after the pattern formation, and the resolution decreases accordingly. What happens is a problem.

In order to prevent such problems, a technique has been proposed in which an ethylenically unsaturated group is introduced into a polyamic acid and three-dimensionally crosslinked between the photopolymerizable compound and the polyamic acid. For example, Patent Documents 3 and 4 disclose a photosensitive resin composition in which a (meth) acryloyl group is bonded to a carboxyl group of a polyamic acid. Patent Document 5 discloses a photosensitive resin composition in which an ethylenically unsaturated group is ionically bonded to a carboxyl group of a polyamic acid or a salt thereof. Further, Patent Document 6 discloses a photosensitive polyamic acid using a diamine component having a photosensitive group.
JP-A 61-243869 JP-A-1-141904 JP 2007-286154 A JP 2006-309202 A JP 2007-249013 A Japanese Patent No. 3941557

  However, although the photosensitive polyamic acid described in Patent Documents 3 and 4 has good patterning properties, the polyimide film obtained from the photosensitive polyamic acid has a large stress, so that warpage occurs in the patterned substrate, and it is formed in multiple layers. In such a case, peeling between layers may occur, making it difficult to use a thick film. Moreover, in patent documents 3 and 4, since the photosensitive group is introduce | transduced into the carboxyl group of polyamic acid, imidation becomes inadequate and there exists a tendency for a raise in a water absorption and a fall in solvent resistance to arise.

  On the other hand, the photosensitive polyamic acid described in Patent Document 5 reduces the stress of the polyimide film obtained therefrom, but when patterning on a metal such as copper, the polyamic acid and the metal form a complex. As a result, the developability tends to decrease. Further, in Patent Document 5, since an ion-bonded photosensitive group is introduced, the affinity between polyamic acid and water is high, and the film may swell during development to cause bleeding. Furthermore, in the photosensitive polyamic acid described in Patent Document 6, imidization proceeds sufficiently, but since the light transmittance is low, the resolution and developability in a thick film tend to be lowered.

  The present invention has been made in view of the above circumstances, and provides a photosensitive resin composition and a photosensitive element capable of obtaining sufficient developability and capable of forming a thick film with high resolution. The purpose is to do.

  The present invention provides (A) a polyamic acid having structural units represented by the following general formulas (1), (2) and (3), (B) a photopolymerizable compound, (C) a photopolymerization initiator, The photosensitive resin composition containing is provided.

ここで、式（１）、（２）及び（３）中、Ａｒ^１はテトラカルボン酸二無水物残基を示し、Ａｒ^２及びＡｒ^３はそれぞれ独立にジアミン残基を示し、Ｒ^１はエチレン性不飽和基を示し、Ａｒ^１及びＡｒ^２の少なくとも一方は主鎖に炭素数５〜２０のアルキレン基を有する。

Here, in the formulas (1), (2) and (3), Ar ¹ represents a tetracarboxylic dianhydride residue, Ar ² and Ar ³ each independently represent a diamine residue, and R ¹ represents ethylene. An unsaturated group, and at least one of Ar ¹ and Ar ² has an alkylene group having 5 to 20 carbon atoms in the main chain.

  In the photosensitive resin composition of the present invention, the (A) polyamic acid has an ethylenically unsaturated group in the side chain, so that (B) the photopolymerizable compound is three-dimensionally crosslinked after exposure, Acid oozing can be sufficiently suppressed and the remaining film rate can be increased. Further, by having an alkylene group having 5 to 20 carbon atoms in the main chain of the polyamic acid, the resolution can be improved, imidization can easily proceed, and the water absorption rate can be reduced. That is, the photosensitive resin composition of the present invention having the above-described configuration can obtain sufficient developability and can form an image with a thick film with high resolution, and can be a thick film on a substrate such as a silicon substrate. Formation is possible. Moreover, according to the said photosensitive resin composition, since it contains a polyimide resin precursor, it can have the cured | curing body which has the outstanding heat resistance, and was excellent also in the electrical property, the mechanical property, etc. Therefore, the photosensitive resin composition of the present invention is very useful for forming a surface protective film and an interlayer insulating film of a semiconductor element.

From the viewpoint of further improving developability and resolution, in the general formula (1), Ar ¹ is preferably a tetravalent group represented by the following general formula (4).

ここで、式（４）中、Ｘは炭素数５〜２０のアルキレン基を示し、Ｒ^２及びＲ^３はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は炭素数１〜３のアルコキシ基を示し、ｍ及びｎはそれぞれ独立に１〜３の整数を示し、ｍが２以上の場合、複数存在するＲ^２は同一でも異なっていてもよく、ｎが２以上の場合、複数存在するＲ^３は同一でも異なっていてもよい。

Here, in formula (4), X represents an alkylene group having 5 to 20 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. And m and n each independently represent an integer of 1 to 3. When m is 2 or more, a plurality of R ² may be the same or different, and when n is 2 or more, a plurality of R ² are present. R ³ may be the same or different.

In the general formula (2), when Ar ² is a divalent group represented by the following general formula (5), imidization at a relatively low temperature is likely to proceed, and the flexibility is excellent. Warpage can be reduced.

ここで、式（５）中、Ｚは単結合又は２価の有機基を示し、Ｙ^１及びＹ^２はそれぞれ独立に炭素数５〜２０のアルキレン基を示す。

Here, in Formula (5), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms.

  In the above general formula (5), Z is preferably at least one group selected from the group consisting of divalent groups represented by the following general formulas (6), (7) and (8). . Thereby, not only is it excellent in developability and resolution, but also the curing temperature after pattern formation can be lowered.

ここで、式（６）、（７）及び（８）中、Ｒ^４、Ｒ^５及びＲ^６は、それぞれ独立に水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑ、ｒ及びｐは、それぞれ独立に１〜４の整数を示し、ｑが２以上の場合、複数存在するＲ^４は同一でも異なっていてもよく、ｒが２以上の場合、複数存在するＲ^５は同一でも異なっていてもよく、ｐが２以上の場合、複数存在するＲ^６は同一でも異なっていてもよい。

Here, in the formulas (6), (7) and (8), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms. Or an alkoxy group having 1 to 3 carbon atoms, q, r and p each independently represent an integer of 1 to 4, and when q is 2 or more, a plurality of R ⁴ may be the same or different. , R is 2 or more, a plurality of R ⁵ may be the same or different, and when p is 2 or more, a plurality of R ⁶ may be the same or different.

  The present invention also provides a photosensitive element comprising a support and a layer made of the photosensitive resin composition formed on the support (hereinafter referred to as “photosensitive layer”). Thus, a non-photosensitive resin composition is applied to form a non-photosensitive layer, and then a photosensitive resin composition is applied onto the non-photosensitive layer to form a photosensitive layer, which is exposed and developed to form a pattern. Thus, it is not necessary to go through such complicated steps, and the process can be shortened. Moreover, since the photosensitive layer is a film, handling becomes easy.

  ADVANTAGE OF THE INVENTION According to this invention, while being able to acquire sufficient developability, the photosensitive resin composition and photosensitive element which can perform image formation with sufficient resolution with a thick film can be provided.

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

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) polyamic acid (hereinafter sometimes referred to as “component (A)”) and (B) a photopolymerizable compound (hereinafter sometimes referred to as “component (B)”). And (C) a photopolymerization initiator (hereinafter sometimes referred to as “component (C)”). Hereinafter, each component will be described in detail.

<(A) component>
The polyamic acid in the present invention has structural units represented by the above general formulas (1), (2) and (3) (hereinafter referred to as “general formulas (1) to (3)”). . Moreover, (A) component may consist only of the structural unit represented by the said general formula (1)-(3), and further comprises structural units other than the said general formula (1)-(3). You may have. Furthermore, as the component (A), a polyamic acid having the structural units represented by the general formulas (1) to (3) may be used alone, or may be used in combination with other polyamic acids.

  These (A) polyamic acids can be produced, for example, by reacting a tetracarboxylic dianhydride component and a diamine component in a solvent.

  Here, at least one of the tetracarboxylic dianhydride component and the diamine component contains an alkylene group having 5 to 20 carbon atoms in the main chain. Thereby, it is possible to provide a photosensitive resin composition capable of obtaining sufficient developability and capable of forming an image with a thick film with high resolution. Moreover, low temperature curability, flexibility, low water absorption and low warpage of the photosensitive resin composition can be achieved by containing an alkylene group having 5 to 20 carbon atoms in the main chain. In the present specification, the term “thick film” refers to a case where the thickness of the coating film formed from the photosensitive resin composition is 20 μm or more.

  Moreover, heat resistance can be improved when at least one of the tetracarboxylic dianhydride component and the diamine component has an aromatic group in the main chain.

  Furthermore, the polyamic acid preferably does not contain an ether bond such as a polyalkyleneoxy group. Since the ether bond is easily broken at a high temperature, the heat resistance may be lowered. Moreover, when it has an ether bond, water absorption increases and an insulation characteristic may be affected.

(Tetracarboxylic dianhydride component)
The tetracarboxylic dianhydride component has a structural unit represented by the general formula (1). In general formula (1), Ar ¹ which is a tetracarboxylic dianhydride residue preferably has an alkylene group having 5 to 20 carbon atoms in the main chain, and is tetravalent represented by the above general formula (4). The organic group is more preferable. Examples of such a tetracarboxylic dianhydride component include a compound represented by the following general formula (9).

ここで、式（９）中、Ｘは炭素数５〜２０アルキレン基を示す。

Here, in Formula (9), X shows a C5-C20 alkylene group.

  Examples of the compound represented by the general formula (9) include pentamethylene bis trimellitate dianhydride, hexamethylene bis trimellitate dianhydride, heptamethylene bis trimellitate dianhydride, octamethylene bis trimellitate dianhydride. Nonamethylene bis trimellitate dianhydride, decamethylene bis trimellitate dianhydride, dodecamethylene bis trimellitate dianhydride. Among these, decamethylene bistrimellitate dianhydride is preferable because the resulting film has low water absorption and low elasticity. These can be used individually by 1 type or in combination of 2 or more types.

  In synthesizing the polyamic acid (A), a tetracarboxylic dianhydride other than the tetracarboxylic dianhydride component having an alkylene group having 5 to 20 carbon atoms in the main chain may be used in combination. Examples of such tetracarboxylic dianhydrides include pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic anhydride. 1,2,4,5-cyclopentanetetracarboxylic acid anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid anhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,3 ′ , 4,4′-bicyclohexyltetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic anhydride (4,4′-oxydiphthalic dianhydride), 2 3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3 ', 4'-diphenyl sulfone tetracarboxylic acid Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] nonane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] decane Water, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] tetradecane Anhydride, 2,2-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2 -Methyldecane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] -2-methyloctane dianhydride, 1,1-bis [4- (3,4-dicarboxy) Benzoyloxy) phenyl] -2-ethylpentadecane dianhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] dodecane Anhydride, 2,2-bis [3,5-dimethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] decane dianhydride, 2,2-bis [3,5-dimethyl-4- (3 , 4-Dicarboxybenzoyloxy) phenyl] tridecane dianhydride, 2,2-bis [3,5-diethyl-4- (3,4-dicarboxybenzoyloxy) phenyl] pentadecane dianhydride, 1,1- Bis [4- (3,4-dicarboxybenzoyloxy) phenyl] cyclohexane dianhydride, 1,1-bis [4- (3,4-dicarboxybenzoyloxy) phenyl] propylcyclohexane dianhydride, 1,1 -Bis [4- (3,4-dicarboxybenzoyloxy) phenyl] heptylcyclohexane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) tetra Ruoropuropan dianhydride, 4,4-bis (2,3-dicarboxyphenoxy) diphenylmethane dianhydride. These are used alone or in combination of two or more.

(Diamine component)
A diamine component has a structural unit represented by the said General formula (2) or (3). In General Formula (2), Ar ² that is a diamine residue preferably has an alkylene group having 5 to 20 carbon atoms in the main chain, and is a divalent organic group represented by General Formula (5). It is more preferable. In the general formula (5), when Z is a divalent organic group, it is selected from the group consisting of divalent organic groups represented by the general formulas (6), (7) and (8), respectively. It is preferably at least one group.

  Examples of the diamine component having an alkylene group having 5 to 20 carbon atoms in the main chain include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 2,11-diaminododecane, 1,12 -Dodecanediamine, 2,5-dimethylhexamethylenediamine, 3-methylheptamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 5-methylnonamethylenediamine, 3-methoxyhexamethylene Examples thereof include aliphatic diamines such as diamines and compounds represented by the following general formulas (10), (11) and (12).

ここで、式（１０）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^７は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｑは１〜４の整数を示す。なお、ｑが２以上の場合、複数存在するＲ^７は同一でも異なっていてもよい。

Here, in Formula (10), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. An alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and q represents an integer of 1 to 4. When q is 2 or more, a plurality of R ⁷ may be the same or different.

ここで、式（１１）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^８は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｒは１〜４の整数を示す。なお、ｒが２以上の場合、複数存在するＲ^８は同一でも異なっていてもよい。

Here, in Formula (11), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁸ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and r represents an integer of 1 to 4. When r is 2 or more, a plurality of R ⁸ may be the same or different.

ここで、式（１２）中、Ｙ^１及びＹ^２は、それぞれ独立に炭素数５〜２０のアルキレン基を示し、Ｒ^９は水素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のアルケニル基又は炭素数１〜３のアルコキシ基を示し、ｓは１〜４の整数を示す。なお、ｓが２以上の場合、複数存在するＲ^９は同一でも異なっていてもよい。

Here, in Formula (12), Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms, R ⁹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms. Alkenyl group or an alkoxy group having 1 to 3 carbon atoms, and s represents an integer of 1 to 4. When s is 2 or more, a plurality of R ⁹ may be the same or different.

  Examples of the diamine component containing the compound represented by the general formula (11) and / or (12) include [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene. (Product name: Versamin 551, manufactured by Cognis Japan Co., Ltd.) is commercially available.

  Moreover, as a diamine component which has a structural unit represented by the said General formula (2), diamine components other than the diamine component which has a C5-C20 alkylene group in a principal chain can be used together. Examples of such a diamine component include 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4 ′. -Diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 4,4' -Tylene bis (cyclohexylamine), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-dimethoxy-4,4'-diaminodiphenylmethane, 3,3'diethoxy-4,4'-diamino Diphenylmethane, bis (3-aminophenyl) ether, bis (4-aminophenyl) ether, 3,4'-diaminodiphe Ether, 3,3′-diethyl-4,4′-diaminodiphenyl ether, 3,3′-dimethoxy-4,4′-diaminodiphenyl ether, bis [4- (4-aminophenoxy) phenyl] ether, 3,3 ′ -Dimethyl-4,4'-diaminodiphenyl sulfone, 3,3'-diethyl-4,4'-diaminodiphenyl sulfone, 3,3'-dimethoxy-4,4'-diaminodiphenyl sulfone, 3,3'-diethoxy -4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylpropane, 3,3'-diethyl-4,4'-diaminodiphenylpropane, 3,3'-dimethoxy-4 , 4′-diaminodiphenylpropane, 3,3′-diethoxy-4,4′-diaminodiphenylpropane, 2,2- [4- (4-aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfide, 3 3,3′-dimethyl-4,4′-diaminodiphenyl sulfide, 3,3′-diethyl-4,4′-diaminodiphenyl sulfide, 3,3′-dimethoxy-4,4′-diaminodiphenyl sulfide, 3,3 '-Diethoxy-4,4'-diaminodiphenyl sulfide, 2,2'-diaminodiethyl sulfide, 2,4'-diaminodiphenyl sulfide, m-phenylenediamine, p-phenylenediamine, 1,3-bis (4-amino Phenoxy) benzene, 1,2-bis (4-aminophenyl) ethane, 1,2-bis (4-aminophen) Nyl) ethane, bis (3-aminophenyl) sulfone, bis (4-aminophenyl) sulfone, o-toluidinesulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, 4,4′-diaminodibenzyl sulfoxide, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, bis (4- Aminophenyl) phenylphosphine oxide, bis (4-aminophenyl) -N-phenylamine, bis (4-aminophenyl) -N-methylamine, 1,2-diaminonaphthalene, 1,4-diaminonaphthalene, 1,5 -Diaminonaphthalene, 1,6-diaminonaphthalene, 1,7-di Aminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 2,6-diaminonaphthalene, 1,4-diamino-2-methylnaphthalene, 1,5-diamino-2-methylnaphthalene, 1,3- Diamino-2-phenylnaphthalene, 9,9-bis (4-aminophenyl) fluorene, 4,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 3,3′-dihydroxy-4,4′-diaminobiphenyl 3,3′-dichloro-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,4′-dimethyl-4,4′-diaminobiphenyl, 3,3 ′ -Dimethoxy-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 2,4-diaminotoluene, 2, -Diaminotoluene, 2,6-diaminotoluene, 3,5-diaminotoluene, 1-methoxy-2,4-diaminobenzene, 1,3-diamino-4,6-dimethylbenzene, 1,4-diamino-2, 5-dimethylbenzene, 1,4-diamino-2-methoxy-5-methylbenzene, 1,4-diamino-2,3,5,6-tetramethylbenzene, 1,4-bis (2-methoxy-4-) Aminopentyl) benzene, 1,4-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,4-bis (4-aminophenoxy) benzene, o-xylenediamine, m-xylenediamine, p-xylene Diamine, 9,10-bis (4-aminophenyl) anthracene, 4-aminophenyl-3-aminobenzoate, 2,2-bis (4-aminophenyl) Hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4 -Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis (4-aminophenyl) -1-phenyl-2,2,2- Trifluoroethane, 1,1-bis [4- (4-aminophenoxy) phenyl] -1-phenyl-2,2,2-trifluoroethane, 1,3-bis (3-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) decafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (5-amino-4-methylphenyl) hexafluoropropane, 1,4-bis (3-aminophenyl) buta Examples include aliphatic dicarboxylic acid dihydrazides such as -1-ene-3-yne, adipic acid dihydrazide, and dodecanedioic acid hydrazide. In addition, a silicon-containing diamine such as dimethylsiloxane diamine (for example, trade name: “LP-7100” manufactured by Shin-Etsu Chemical Co., Ltd.) can be used as a part of the diamine component. Among these, 4,4′-diaminodiphenyl sulfone is preferably used because alkali solubility is improved and developability is improved. In addition, since the resolution can be further improved, it is also preferable to use an aliphatic dicarboxylic acid dihydrazide such as adipic acid dihydrazide or dodecanedioic acid hydrazide. These diamine components may be used alone or in combination of two or more.

  (A) In the polyamic acid, the content of the diamine component having the structural unit represented by the general formula (2) is preferably 50 to 99 mol%, and preferably 60 to 98 mol% with respect to the total amount of the diamine component. Is more preferable, and it is still more preferable that it is 70-97 mol%. Compared with the case where the content of the diamine component having the structural unit represented by the general formula (2) is out of the above range, developability and resolution tend to be improved.

In the general formula (3), the Ar ³ is a diamine residue, an arylene group is preferred, as the arylene group include a phenylene group. R ¹ bonded to Ar ³ and shown as an ethylenically unsaturated group includes, for example, allyloxy group, (meth) acryloyloxyalkoxyl group, maleimidylalkoxy group, (meth) acryloyloxyalkylamino group, maleic group Examples include a midylalkylamino group, an allyl group, a (meth) acryloyloxyalkyl group, and an ethynyl group. As R ^1, particularly preferably a group represented by the following general formula (I) ~ (IV).

ここで、Ｒ^１０は２価の有機基を示し、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４及びＲ^１５は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基、フェニル基、ビニル基又はプロペニル基を示す。Ｒ^１０としては、メチレン基、エチレン基、プロピレン基等の炭素数１〜４のアルキレン基であることが好ましい。

Here, R ¹⁰ represents a divalent organic group, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, vinyl Represents a group or a propenyl group. R ¹⁰ is preferably an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, or a propylene group.

  Examples of the diamine component having the structural unit represented by the general formula (3) are represented by the following formulas (21), (22), (23), (24), (25), and (26). Compounds.

  Among these, use of methacryloylethyl-3,5-diaminobenzoate represented by the formula (22) is preferable because it can reduce bleeding and film thickness reduction during development. A commercially available product is “BEM-S” (trade name, manufactured by Kawaken Fine Chemical Co., Ltd., methacryloylethyl-3,5-diaminobenzoate). Moreover, these diamine compounds may be used alone or in combination of two or more.

  (A) In the polyamic acid, the content of the diamine component having the structural unit represented by the general formula (3) is preferably 1 to 50 mol%, and 2 to 40 mol% with respect to the total amount of the diamine component. It is more preferable, and it is further more preferable that it is 3-30 mol%. Compared with the case where the content of the diamine component having the structural unit represented by the general formula (3) is outside the above range, the elongation of the film after curing tends to decrease or the elastic modulus tends to increase.

  (A) The polyamic acid can introduce the structural unit represented by the general formula (3) by using the above-described diamine component having an ethylenically unsaturated group. Moreover, after synthesizing a polyamic acid without using a diamine component having an ethylenically unsaturated group, an ethylenically unsaturated group can also be introduced. However, in the latter method, an ethylenically unsaturated group may be bonded to the carboxyl group of the polyamic acid, which may prevent imidization during curing and lead to an increase in water absorption. For this reason, it is preferable to obtain the polyamic acid which has an ethylenically unsaturated group in a side chain more simply by making the diamine component which has an ethylenically unsaturated group, and the tetracarboxylic dianhydride component react. And (A) polyamic acid has the structural unit represented by General formula (3), and at the time of exposure and post-exposure heating (PEB), (A) polyamic acid and (B) photopolymerizable compound Covalent bonds are formed between them, resulting in three-dimensional crosslinking. Therefore, swelling and bleeding at the time of development are sufficiently suppressed.

(Method for synthesizing polyamic acid)
(A) The polyamic acid is synthesized from the diamine component and the tetracarboxylic dianhydride component by a known method. That is, it is synthesized by selectively combining a tetracarboxylic dianhydride component and a diamine component and causing a polymerization reaction in an organic solvent. Specifically, (A) the polyamic acid is obtained by mixing an approximately equimolar amount of a tetracarboxylic dianhydride component and a diamine component in an organic solvent at a reaction temperature of 160 ° C. or lower, preferably 60 ° C. or lower for 1 to 12 hours. It can be obtained by addition polymerization reaction.

  Examples of the solvent include nitrogen-containing solvents (N, N′-dimethylsulfoxide, N, N′-dimethylformamide, N, N′-diethylformamide, N, N′-dimethylacetamide, N, N′- Diethylacetamide, N-methyl-2-pyrrolidone, hexamethylenephosphoamide, N-methylpyrrolidone, etc.), lactones (γ-butyrolactone, γ-valerolactone, γ-caprolactone, ε-caprolactone, α-acetyl-γ-butyrolactone Etc.), alicyclic ketones (cyclohexanone, 4-methylcyclohexanone, etc.), ethers (3-methyl-3-methoxybutyl acetate, diethylene glycol dimethyl ether acetate, etc.). Among these, lactones, alicyclic ketones, and ethers are preferable from the viewpoint of solubility and water absorption, and γ-butyrolactone is particularly preferable. These are used individually by 1 type or in combination of 2 or more types.

  The combination of the tetracarboxylic dianhydride component and the diamine component is preferably selected from the components described above in consideration of the heat resistance, mechanical properties, and electrical properties of the polyimide resin film after final curing.

  Moreover, in order to improve the adhesiveness and developability of (A) polyamic acid, it is preferable to introduce aminobenzimidazole or a derivative thereof into (A) polyamic acid. Examples of aminobenzimidazole and derivatives thereof include 2-aminobenzimidazole, 2-amino-6-methyl-benzimidazole, 2-amino-6-ethyl-benzimidazole, 2-amino-6-butyl-benzimidazole, 2-amino-6-nitro-benzimidazole is mentioned. Among these, 2-amino-benzimidazole is preferable from the viewpoint of adhesiveness.

  The amount introduced when aminobenzimidazole or a derivative thereof is introduced is preferably 0.1 to 10 mol, more preferably 1 to 5 mol, based on 100 mol of (A) polyamic acid. Particularly preferred is 3 moles. If the introduction amount of aminobenzimidazole or a derivative thereof is less than 0.1 mol, the effect of improving adhesiveness tends to be insufficient, and if it exceeds 10 mol, developability and storage stability tend to be lowered.

  The weight average molecular weight of the polyamic acid as the component (A) is preferably 10,000 to 60,000, and more preferably 20,000 to 50,000. If the weight average molecular weight is less than 10,000, the cured film tends to be brittle, and if it exceeds 60,000, the developability tends to decrease.

  In the photosensitive resin composition, the content of (A) polyamic acid is preferably 20 to 80 parts by mass, and preferably 30 to 70 parts by mass based on 100 parts by mass of the total of components (A) and (B). It is more preferable that it is 35-65 mass parts. If the content is less than 20 parts by mass, the developability tends to decrease, and if it exceeds 80 parts by mass, the resolution tends to decrease or the imidization rate at low temperatures tends to decrease.

<(B) component>
Next, the component (B) will be described.

  The component (B) is not particularly limited as long as it is a photopolymerizable compound having an ethylenically unsaturated group. For example, a compound obtained by reacting a polyhydric alcohol with an α, β-unsaturated carboxylic acid, bisphenol A Urethane monomers such as system (meth) acrylate compounds, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, photopolymerizable compounds having urethane bonds and ethylenically unsaturated groups in the molecule, Nonylphenoxypolyethyleneoxyacrylate, phthalic acid compounds, and (meth) acrylic acid alkyl esters are exemplified. These are used singly or in combination of two or more. In addition, (B) a photopolymerizable compound may be synthesize | combined by a conventional method, and a commercially available thing may be obtained.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, polyethylene polypropylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 14 propylene groups, trimethylolpropane di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meta) ) Acrylate, tetramethylolmethane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, neopentyl glycol diacrylate, and nonanediol diacrylate. These are used singly or in combination of two or more. Here, “EO” represents ethylene oxide, and an EO-modified compound represents one having a block structure of an ethylene oxide group. “PO” represents propylene oxide, and a PO-modified compound has a propylene oxide group block structure.

  Neopentyl glycol diacrylate is commercially available as A-NPG (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.), and nonanediol diacrylate is FA-129 (trade name, Hitachi Chemical Co., Ltd.). It is commercially available as).

  Examples of the bisphenol A-based (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxypoly). Propoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane, etc. Is mentioned. Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2 , 2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl) propane, 2,2-bis (4- ((Meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxy) Hexadecaethoxy) phenyl) propane. These are used individually by 1 type or in combination of 2 or more types.

  Of these, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Bis (4- (methacryloxypentadecaethoxy) phenyl) propane is commercially available as BPE-1300 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  The photopolymerizable compound having a urethane bond and an ethylenically unsaturated group in the molecule has, for example, a urethane bond derived from a reaction between a dihydroxyl group and an isocyanate group of a diisocyanate compound, and an isocyanate group at a plurality of terminals. It can be obtained by subjecting a urethane compound having a hydroxyl group and an ethylenically unsaturated group to a condensation reaction.

  Examples of available photopolymerizable compounds having a urethane bond and an ethylenically unsaturated group in the molecule include TMCH-5 (trade name, manufactured by Hitachi Chemical Co., Ltd.), Hitaroid 9082 (trade name, Hitachi Chemical Co., Ltd.). Company-made), UA-11, UA-21 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Examples of the compound obtained by reacting the glycidyl group-containing compound with an α, β-unsaturated carboxylic acid include a novolac epoxy resin represented by the following general formula (13) and a bisphenol represented by the following general formula (14). Reaction of at least one epoxy resin selected from the group consisting of a type A epoxy resin or a bisphenol F type epoxy resin and a salicylaldehyde type epoxy resin represented by the following general formula (15) with a vinyl group-containing monocarboxylic acid It is preferable that the resin obtained by making it contain.

ここで、Ｒ^２０は水素原子又はメチル基を示し、Ｙ^１は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ１は１以上の整数を示す。なお、複数存在するＲ^２０及びＹ^１はそれぞれ同一でも異なっていてもよい。

Here, R ²⁰ represents a hydrogen atom or a methyl group, Y ¹ represents a hydrogen atom or a glycidyl group (however, a hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n1 is 1 The above integers are shown. A plurality of R ²⁰ and Y ¹ may be the same or different.

ここで、Ｒ^２１は水素原子又はメチル基を示し、Ｙ^２は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^２１及びＹ^２はそれぞれ同一でも異なっていてもよい。

Here, R ²¹ represents a hydrogen atom or a methyl group, Y ² represents a hydrogen atom or a glycidyl group (however, a hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n2 is 1 The above integers are shown. A plurality of R ²¹ and Y ² may be the same or different.

ここで、式中、Ｙ^３は水素原子又はグリシジル基（ただし、水素原子／グリシジル基（モル比）は、０／１００〜３０／７０）を示し、ｎ３は１以上の整数を示す。なお、複数存在するＹ^３はそれぞれ同一でも異なっていてもよい。

Here, in the formula, Y ³ represents a hydrogen atom or a glycidyl group (wherein hydrogen atom / glycidyl group (molar ratio) is 0/100 to 30/70), and n3 represents an integer of 1 or more. A plurality of Y ³ may be the same or different.

  Examples of the novolak type epoxy resin represented by the general formula (13) include a phenol novolak type epoxy resin and a cresol novolak type epoxy resin. These novolak type epoxy resins can be obtained by reacting a phenol novolak resin and a cresol novolak resin with epichlorohydrin, respectively, by a known method.

In the compound represented by the general formula (14), the bisphenol A type epoxy resin or bisphenol F type epoxy resin in which Y ² is a glycidyl group is, for example, a bisphenol A type epoxy represented by the following general formula (16). It can be obtained by reacting the hydroxyl group of the resin or bisphenol F type epoxy resin with epichlorohydrin.

ここで、Ｒ^２１は水素原子又はメチル基を示し、ｎ２は１以上の整数を示す。なお、複数存在するＲ^２１はそれぞれ同一でも異なっていてもよい。

Here, R ²¹ represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or more. A plurality of R ²¹ may be the same or different.

  In order to promote the reaction between the hydroxyl group and epichlorohydrin, the reaction is preferably carried out in a polar organic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide in the presence of an alkali metal hydroxide at a reaction temperature of 50 to 120 ° C. If the reaction temperature is less than 50 ° C., the reaction is slow, and if the reaction temperature exceeds 120 ° C., many side reactions occur, which is not preferable.

  Specific examples of the salicylaldehyde type epoxy resin represented by the general formula (15) include FAE-2500, EPPN-501H, and EPPN-502H (trade name, manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the vinyl group-containing monocarboxylic acid include acrylic acid, dimer of acrylic acid, methacrylic acid, β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and α-cyanocinnamic acid. Can be mentioned. In addition, a half-ester compound, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester and a saturated or unsaturated dibasic acid anhydride, which is a reaction product of a hydroxyl group-containing acrylate and a saturated or unsaturated dibasic acid anhydride The half-ester compound which is a reaction product of is mentioned. These half ester compounds are obtained by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a saturated or unsaturated dibasic acid anhydride in an equimolar ratio. These vinyl group-containing monocarboxylic acids can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used in the synthesis of the half ester compound include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate. , Hydroxybutyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol pentamethacrylate, Guri Jill acrylate, glycidyl methacrylate.

  Examples of the saturated or unsaturated dibasic acid anhydride used in the synthesis of the half ester compound include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, and ethyltetrahydrophthalic anhydride. Examples thereof include acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

  In the reaction between the epoxy resin and the vinyl group-containing monocarboxylic acid, it is preferable that the vinyl group-containing monocarboxylic acid is reacted at a ratio of 0.8 to 1.05 equivalent to 1 equivalent of the epoxy group of the epoxy resin. More preferably, it is 0.9 to 1.0 equivalent.

  The epoxy resin and the vinyl group-containing monocarboxylic acid can be dissolved in an organic solvent and reacted. Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate, aliphatic carbonization such as octane and decane Examples thereof include petroleum solvents such as hydrogen, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.

  Further, it is preferable to use a catalyst in order to promote the reaction. Examples of the catalyst used include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylmethylammonium iodide, and triphenylphosphine. The usage-amount of a catalyst becomes like this. Preferably it is 0.1-10 mass parts with respect to a total of 100 mass parts of an epoxy resin and vinyl group containing monocarboxylic acid.

  Moreover, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol, and the amount used is preferably 0 with respect to a total of 100 parts by mass of the epoxy resin and the vinyl group-containing monocarboxylic acid. 0.01 to 1 part by mass. The reaction temperature is preferably 60 to 150 ° C, more preferably 80 to 120 ° C.

  If necessary, a vinyl group-containing monocarboxylic acid and a polybasic acid anhydride such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like can be used in combination.

  The vinyl group-containing epoxy resin, which is a resin obtained by reacting the epoxy resins represented by the general formulas (13) to (15) with a vinyl group-containing monocarboxylic acid, improves the solubility in a developer. Alternatively, a resin obtained by reacting a saturated or unsaturated group-containing polybasic acid anhydride may be used.

  Examples of saturated or unsaturated group-containing polybasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Examples include methylhexahydrophthalic anhydride, ethylhexahydrophthalic anhydride, and itaconic anhydride.

  In the reaction of the saturated or unsaturated group-containing polybasic acid anhydride with the vinyl group-containing epoxy resin, 0 to 1.0 equivalent of the saturated or unsaturated group-containing polybasic acid anhydride is reacted with 1 equivalent of the hydroxyl group. Thus, an acid-modified vinyl group-containing epoxy resin can be obtained.

  The acid value of the acid-modified vinyl group-containing epoxy resin (A) is preferably 1 to 150 mgKOH / g, more preferably 5 to 100 mgKOH / g, and still more preferably 10 to 70 mgKOH / g. When the acid value exceeds 150 mgKOH / g, the film tends to swell during development or the water absorption rate of the film tends to increase. When the acid value is less than 1 mgKOH / g, undissolved residue tends to occur at the bottom of the pattern.

  As a photopolymerizable compound having an acid-modified vinyl group-containing epoxy resin that can be obtained, for example, Hitaroid 7661 (trade name, manufactured by Hitachi Chemical Co., Ltd.), KAYARAD CCR-1159 (trade name, manufactured by Nippon Kayaku Co., Ltd.) , KAYARAD TCR-1310 (manufactured by Nippon Kayaku Co., Ltd., trade name).

  Among these, as component (B), (A) a hyaloid which is an acid-modified novolak resin containing a vinyl group from the viewpoint of compatibility with polyamic acid, solubility in a developer, and heat resistance of a cured film 7661 is preferred. These may be used alone or in combination of two or more.

  In the photosensitive resin composition, the content of the component (B) is preferably 20 to 80 parts by weight, based on a total of 100 parts by weight of the component (A) and the component (B), and 30 to 70 parts by weight. It is more preferable that it is 35-65 mass parts. When the content is less than 20 parts by mass, the resolution tends to decrease or the imidization rate at low temperature tends to decrease. When the content exceeds 80 parts by mass, the content is within the above range. Compared to the above, the developability tends to be lowered.

<(C) component>
The photopolymerization initiator as component (C) is not particularly limited as long as it generates a free radical by active light. For example, aromatic ketone, quinones, benzoin ether compound, benzyl derivative, 2, 4, 5 -Triarylimidazole dimer, acridine derivative, N-phenylglycine, N-phenylglycine derivative, phosphine oxide derivative, oxime ester derivative, coumarin compound.

  Examples of the aromatic ketone include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (that is, Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4. '-Dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- Propan-1-one is mentioned.

  Examples of quinones include 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenyl. Examples include anthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone.

  Examples of the benzoin ether compound include benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether. Examples of commercially available products include Irgacure-369 and Irgacure-907 (trade name, manufactured by Ciba Specialty Chemicals).

  Examples of the benzyl derivative include benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, and benzyldimethyl ketal. Examples of commercially available products include Irgacure-651 (trade name, manufactured by Ciba Specialty Chemicals), which is benzyldimethyl ketal.

  Examples of the 2,4,5-triarylimidazole dimer include 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl) -4,5-diphenyl-1,3-diazol-2- Yl] -4,5-diphenylimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer is mentioned.

  Examples of the acridine derivative include 9-phenylacridine and 1,7-bis (9,9'-acridinyl) heptane.

  Examples of the phosphine derivative include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Examples of commercially available products include Darocur-TPO (trade name, manufactured by Ciba Specialty Chemicals) which is 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

  Examples of the oxime ester derivative include 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) -1,2-octanedione.

  (C) A photoinitiator may be synthesize | combined by a conventional method and a commercially available thing may be obtained. Examples of commercially available (C) photopolymerization initiators include Darocur-TPO, Irgacure-369, Irgacure-907, Irgacure-651, Irgacure-819, Irgacure-OXE-01 (all of which are Ciba Specialty. Chemicals, product name).

  Among the above-described (C) photopolymerization initiators, Irgacure-651 and Irgacure-OXE-01 are particularly preferable from the viewpoint of improving sensitivity and compatibility with a solvent. The said (C) photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  In the photosensitive resin composition of the present invention, the content of (C) the photopolymerization initiator is preferably 1 to 20% by mass, based on the total solid content of the photosensitive resin composition, and preferably 2 to 10% by mass. % Is more preferable, and 2.5 to 8% by mass is particularly preferable. (C) When the content of the photopolymerization initiator is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility is decreased as compared with the case where the content is in the above range. There is a tendency.

<Other ingredients>
((D) Crosslinking agent)
Moreover, you may add (D) crosslinking agent further to the photosensitive resin composition of this invention. (D) Although it does not restrict | limit especially as a crosslinking agent, An epoxy compound, a blocked isocyanate compound, etc. are mentioned. Specifically, YH-434L (amine type epoxy resin, manufactured by Tohto Kasei Co., Ltd., trade name) is preferable as the epoxy compound. Specifically, BL-3175 (blocked isocyanate, manufactured by Sumika Bayer Urethane Co., Ltd., trade name) is preferable as the blocked isocyanate compound. When these crosslinking agents are added, the adhesiveness of the cured photosensitive resin composition to the substrate can be further improved.

  When (D) a crosslinking agent is contained in the photosensitive resin composition, the content is preferably 10 to 60 parts by mass, and 30 to 40 parts by mass with respect to 100 parts by mass of (A) polyamic acid. More preferably. When the content of the (D) crosslinking agent is out of the above range, the cured film after curing becomes fragile as compared with the case where the content is within the above range, or (A) the polyamic acid and (D) the crosslinking agent. There is a tendency that the compatibility with is reduced.

((E) sensitizer)
Further, (E) a sensitizer can be further added to the photosensitive resin composition of the present invention. Examples of (E) sensitizers include Michler's ketone, 4,4-diethylaminobenzophenone, 3,3′-carbonylbis (diethylaminocoumarin), and the like. (E) As a sensitizer, from the viewpoints of sensitivity of the photosensitive resin composition and compatibility with a solvent, coumarins are preferable, and Coumarin 102 (trade name, manufactured by Acros Co., Ltd.) is particularly preferable. (E) A sensitizer is used individually by 1 type or in mixture of 2 or more types.

  The content of the (E) sensitizer in the photosensitive resin composition is preferably 0.1 to 1% by mass based on the total solid content of the photosensitive resin composition. (E) When the content of the sensitizing dye is out of the above range, the sensitivity of the photosensitive resin composition is decreased or the compatibility with the solvent is decreased as compared with the case where the content is within the above range. There is a tendency to.

  The photosensitive resin composition of the present invention comprises (A) a polyamic acid, (B) a photopolymerizable compound and (C) a photopolymerization initiator, and (D) a crosslinking agent and / or ( E) It can be obtained by mixing a sensitizer with a solvent.

(solvent)
The solvent used at this time is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, propylene glycol monomethyl ether acetate, and γ-butyrolactone. These solvents are used alone or as a mixture of two or more.

(Adhesion aid)
If necessary, an adhesion assistant may be added to the photosensitive resin composition in order to improve the adhesion between the photosensitive resin composition and the substrate. Examples of the adhesion assistant include silane coupling agents such as γ-glycidoxysilane, aminosilane, γ-ureidosilane, and 3-methacryloxypropyltrimethoxysilane. Commonly available adhesion assistants include KBM-503 (3-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone, trade name), AY-43031 (γ-ureidopropyltriethoxysilane, manufactured by Toray Dow Co., Ltd.) , Product name). These may be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention obtained as described above can obtain sufficient developability and can perform image formation with a thick film with high resolution. It can be used as a surface protective film or an interlayer insulating film of a semiconductor element.

[Pattern formation method]
A method for forming a cured body (cured film) using the photosensitive resin composition of the present invention will be described.

  First, the photosensitive resin composition is applied on a substrate. As the substrate, silicon, alumina ceramic, glass, glass ceramic, aluminum nitride, a substrate on which a semiconductor is formed, or the like is used. Examples of the coating method include, but are not limited to, spin coating using a spinner, spray coating, dipping, and roll coating.

  The coating thickness varies depending on the coating means, the solid content concentration and the viscosity of the photosensitive resin composition, and the like. For use as an interlayer insulating film, the film thickness of the dried film (photosensitive resin composition layer) is preferably 1 to 300 μm, more preferably 15 to 150 μm, and particularly preferably 20 to 100 μm. preferable. In order to make the film thickness after drying become 1 to 300 μm, it is preferable to dissolve the photosensitive resin composition of the present invention with a solvent and adjust the viscosity to 1 to 50 Pa · s, preferably 20 to 20 μm. It is more preferable to adjust to 40 Pa · s. The solid content concentration of the photosensitive resin composition is preferably 20 to 80% by mass, and more preferably 30 to 70% by mass. When the film thickness of the obtained film exceeds 300 μm, the resolution tends to decrease.

  Next, the substrate coated with the photosensitive resin composition is dried to obtain a photosensitive resin composition layer made of the photosensitive resin composition. Drying is preferably carried out in the range of 60 to 120 ° C. for 1 minute to 1 hour using an oven, a hot plate or the like.

  Next, a mask having a desired pattern is placed on the photosensitive resin composition layer as necessary, and exposure is performed by irradiating actinic rays through the mask. Examples of the actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, and X-rays. Among these, ultraviolet rays and visible rays are particularly preferable.

  A pattern can be formed by removing an unexposed part using a developing solution after exposure. Here, as the developer, an organic solvent such as N-methylpyrrolidone or ethanol, or an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide or the like is used. Can do. Among these, since there are few metallic ion compounds, it is preferable to use tetramethylammonium hydroxide for development of the photosensitive resin composition.

  Further, after the development, if necessary, rinse with water or an alcohol such as methanol, ethanol, isopropyl alcohol or the like.

  Furthermore, after the development, a cured product made of the photosensitive resin composition can be obtained by curing. In the curing after development, it is preferable to adjust the heating temperature as appropriate, for example, it is preferable to carry out for 1 to 2 hours while raising the temperature stepwise. The heating temperature is preferably adjusted between 120 and 225 ° C. Specifically, after development, for example, heat treatment is performed at 120 ° C., 150 ° C., and 180 ° C. for 20 minutes, and then heat treatment is performed at 225 ° C. for 40 minutes to further heat cure the pattern after photocuring. A cured product can be obtained.

  In addition, the photosensitive resin composition of this invention can also be used with the form of the photosensitive element in which the photosensitive resin composition layer which consists of a photosensitive resin composition was formed on the support body. A photosensitive element is provided with a support body and the layer which consists of the photosensitive resin composition of this invention formed on this support body. When using the photosensitive element in the above-described process, the photosensitive element is disposed so that the photosensitive resin composition layer is in contact with the substrate, and a predetermined portion of the photosensitive resin composition layer is irradiated with active light, thereby the photosensitive resin composition. After the photocured portion is formed on the physical layer, the support can be peeled off and developed.

  The cured body formed from the photosensitive resin composition according to the present invention is useful as a surface protective film or an interlayer insulating film of a semiconductor element.

  FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor package using a cured body formed of the photosensitive resin composition of the present invention as an interlayer insulating film. In the semiconductor package 10 shown in FIG. 1, an electrode 2 made of a metal such as aluminum is provided on a silicon wafer (substrate) 1. The silicon wafer 1 and the electrode 2 are covered with an interlayer insulating film 3, but a part of the interlayer insulating film 3 on the electrode 2 is removed, and is made of a metal such as copper connected to the electrode 2 from the part. The rewiring 4 is drawn out. The rewiring 4 is connected to a post portion 5 made of a metal such as copper. The interlayer insulating film 3, the rewiring 4, and the post portion 5 are sealed with a sealing resin 6 so that only one end of the post portion 5 is exposed.

  In the semiconductor package 10, the interlayer insulating film 3 is formed using the above-described photosensitive resin composition of the present invention. Therefore, the interlayer insulating film 3 is thickened with high resolution and has excellent heat resistance, insulation, and flexibility.

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

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

[Synthesis of polyamic acid]
(Synthesis Example 1)
In a 200 mL four-neck separable flask, “Versamine 551” (trade name, manufactured by Cognis Japan Co., Ltd.) 6.79 g (12.2 mmol), 1.35 g (5.5 mmol) of 4,4′-diaminodiphenylsulfone, 10.00 g (19.1 mmol) of 10- (decamethylene) bis (trimellitate) dianhydride, 0.14 g (0.5 mmol) of methacryloylethyl-3,5-diaminobenzoate and 19 g of N-methylpyrrolidone were added, And stirred. The reaction solution was stirred for 3 hours to obtain an N-methylpyrrolidone (hereinafter referred to as “NMP”) solution of polyamic acid. Solid content in the obtained solution was 50 mass%, the weight average molecular weight (Mw) of polyamic acid was 34000, and dispersity (Mw / Mn) was 2.0. “Versamine 551” is a diamine compound including a compound represented by the following formula (27) and / or a compound in which an unsaturated portion of the compound represented by the following formula (27) is hydrogenated.

(Synthesis Example 2)
In a 200 mL four-necked separable flask, 6.79 g (12.2 mmol) of “Versamine 551”, 1.26 g (5.1 mmol) of 4,4′-diaminodiphenylsulfone, 1,10- (decamethylene) bis (trimellitate) 10.00 g (19.1 mmol) of dianhydride, 0.24 g (0.9 mmol) of methacryloylethyl-3,5-diaminobenzoate and 19 g of N-methylpyrrolidone were added and stirred at 60 ° C. The reaction solution was stirred for 3 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 50 mass%, Mw of polyamic acid was 42000, and dispersion degree was 2.3.

(Synthesis Example 3)
In a 200 mL four-necked separable flask, 6.79 g (12.2 mmol) of “Versamine 551”, 1.04 g (4.2 mmol) of 4,4′-diaminodiphenylsulfone, 1,10- (decamethylene) bis (trimellitate) 10.00 g (19.1 mmol) of dianhydride, 0.48 g (1.8 mmol) of methacryloylethyl-3,5-diaminobenzoate and 19 g of N-methylpyrrolidone were added and stirred at 60 ° C. The reaction solution was stirred for 3 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 50 mass%, Mw of polyamic acid was 38000, and dispersion degree was 2.7.

(Synthesis Example 4)
In a 200 mL four-necked separable flask, 6.79 g (12.2 mmol) of “Versamine 551”, 0.59 g (2.4 mmol) of 4,4′-diaminodiphenylsulfone, 1,10- (decamethylene) bis (trimellitate) 10.00 g (19.1 mmol) of dianhydride, 0.96 g (3.6 mmol) of methacryloylethyl-3,5-diaminobenzoate and 19 g of N-methylpyrrolidone were added and stirred at 60 ° C. The reaction solution was stirred for 3 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 50 mass%, Mw of polyamic acid was 49000, and dispersion degree was 2.7.

(Synthesis Example 5)
To a 200 mL four-necked separable flask, add 15.73 g (28.2 mmol) of “Versamine 551”, 3.31 g (13.3 mmol) of 4,4′-diaminodiphenylsulfone, and 30.0 g of N-methylpyrrolidone. Stir at room temperature for 15 minutes. Next, a mixed solution of 22.24 g (42.6 mmol) of 1,10- (decamethylene) bis (trimellitate) dianhydride and 30.00 g of N-methylpyrrolidone was added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, Mw of polyamic acid was 29000, and dispersion degree was 1.7.

(Synthesis Example 6)
Add 2.31 g (12.5 mmol) of 1,12-dodecanediamine, 1.41 g (5.7 mmol) of 4,4′-diaminodiphenylsulfone and 5.0 g of N-methylpyrrolidone to a 300 mL four-necked separable flask. And stirred at room temperature for 15 minutes. Next, a mixed solution of 10.00 g (19.1 mmol) of 1,10- (decamethylene) bistrimellitic dianhydride and 10.00 g of N-methylpyrrolidone was added over 15 minutes. After completion of the addition, the resulting mixture was heated to 60 ° C. and stirred for 8 hours to obtain an NMP solution of polyamic acid. Solid content in the obtained solution was 40 mass%, Mw of polyamic acid was 48000, and dispersion degree was 3.1.

(Molecular weight measurement)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polyamic acid synthesized in Synthesis Examples 1 to 6 are measured by gel permeation chromatography (GPC) and calculated by a calibration curve using standard polystyrene. It was. The GPC conditions are shown below.

(GPC conditions)
Detector: L-2400 UV-vis Detector (manufactured by Hitachi, Ltd., trade name)
Pump: L-2130 Pump (manufactured by Hitachi, Ltd., trade name)
D-2520 Integrator (manufactured by Hitachi, Ltd., trade name)
Column: Gelpack GL-S300MDT-5 (two in total) (manufactured by Hitachi Chemical Co., Ltd., trade name)
Eluent: THF / DMF = 1/1 (volume ratio) + LiBr (0.03 mol / L) + phosphoric acid (0.06 mol / L)
Flow rate: 1 mL / min

[Preparation of photosensitive resin composition]
The (A) polyamic acid solution synthesized in each of the above synthesis examples, (B) the photopolymerizable compound (C) the photopolymerization initiator, and other components were mixed at the blending ratio (parts by mass) shown in Table 1 below. Thus, a solution of the photosensitive resin composition was obtained. In addition, the number in Table 1 has shown the mass part of solid content. Moreover, each component in Table 1 is shown below.

“Hitaroid 7661”: acid-modified phenol novolac epoxy acrylate, manufactured by Hitachi Chemical Co., Ltd., trade name “I-651”: benzyldimethyl ketal, manufactured by Ciba Specialty Chemicals, trade name “I-OXE-01”: 1, 2-octanedione-1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), manufactured by Ciba Specialty Chemicals, trade name “KBM-503”: 3-methacryloxypropyltrimethoxysilane, east Product name “AY-43031” manufactured by Redau Co., Ltd .: γ-ureidopropyltriethoxysilane, manufactured by Shin-Etsu Silicone Co., Ltd., product name “MDAP”: 3-dimethylaminopropyl methacrylate, manufactured by Hitachi Chemical Co., Ltd., product name “BEM”: Methacryloylethyl-3,5-diaminobenzoate, Kawakenhwa Nkemikaru Co., Ltd., trade name

＊ＢＥＭ導入量は、ジアミン成分全量に対するＢＥＭのモル％を示す。

* BEM introduction amount indicates mol% of BEM with respect to the total amount of diamine component.

<Film-forming evaluation>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a 5-inch silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive resin having a film thickness of 70 μm. A composition layer was formed and the appearance of the coating film was evaluated.
A: There is no cloudiness and tack.
B: The flatness is poor.
C: There is cloudiness.

  When the photosensitive resin composition layer is cloudy, it is considered that the compatibility of the photosensitive resin composition components is poor and is precipitated in the photosensitive resin composition layer.

<Dissolution rate evaluation>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive resin composition having a thickness of 70 μm. A layer was formed. An aqueous 2.38 mass% tetramethylammonium hydroxide solution was dropped into the photosensitive resin composition layer, the time taken for the film to completely dissolve was measured, and the dissolution rate was determined by the following formula (b).
Dissolution rate (nm / second) = film thickness (nm) / dissolution time (second) (b)

<Developability evaluation>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive resin composition having a thickness of 70 μm. A layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, a proximity exposure machine (USHIO Corporation make, brand name) is passed through the negative mask which has a wiring pattern whose line width / space width is 50/400 (unit: micrometer). : UX-1000SM), the photosensitive resin composition layer was exposed at an exposure amount of 500 mJ / cm ² . Here, as for the exposure amount, the illuminance of light, the UV integrated light meter (made by USHIO INC., Trade name “UIT-150-A”, also usable as illuminometer) and “UVD-S365” which is a light receiver. (Sensitivity wavelength range: 320 nm to 470 nm, absolute calibration wavelength: 365 nm) and measured from the relationship of exposure amount = illuminance × exposure time. Thereafter, the test substrate was immersed in an aqueous 2.38% by mass tetramethylammonium hydroxide solution and developed until the unexposed portion of the photosensitive resin composition layer was completely dissolved. The film loss of the exposed part of the photosensitive resin composition layer after development was measured, and developability was evaluated based on the following evaluation criteria. The results are shown in Table 2.
A: The film reduction in the exposed area is less than 10%.
B: The film reduction in the exposed area is 10% or more and less than 80%.
C: Film reduction in the exposed area is 80% or more.

<Evaluation of resolution>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive resin composition having a thickness of 70 μm. A layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, after exposing the photosensitive resin composition layer by the exposure amount of 500 mJ / cm < ² > through the negative pattern for resolution evaluation made from a photochemical company, small developing machine " Development was performed by a paddle method using “AD-1200” (trade name, manufactured by MIKASA), and the L / S = 60/60 pattern after development was observed with a metal microscope manufactured by Olympus.
A: No residue or exudation B: Residue or exudation C: Swelled

<Measurement of elastic modulus and elongation>
The photosensitive resin composition solutions of the above examples and comparative examples were uniformly applied on a silicon substrate using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive resin composition having a thickness of 70 μm. A layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, the whole surface exposure was performed by the exposure amount of 500 mJ / cm < ² > using the proximity exposure machine (Ushio Electric make, brand name: UX-1000SM). Then, it was cured by heating at 120 ° C. for 40 minutes and then at 200 ° C. for 60 minutes to obtain a cured film having a thickness of 50 μm. The cured film was peeled from the silicon substrate to produce a 1 cm × 5 cm test piece. With respect to this test piece, the tensile modulus and elongation were measured using a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph AGF-5KN) at a temperature of 23 ° C., a chuck distance of 20 mm, and a tensile speed of 5 mm / min. .

<Measurement of water absorption rate>
The photosensitive resin composition solutions of the above Examples and Comparative Examples were uniformly applied onto a glass plate having a thickness of 1 mm using a spin coater, dried on a hot plate at 110 ° C. for 5 minutes, and a photosensitive film having a thickness of 70 μm. A functional resin composition layer was formed. About the test board | substrate which formed this photosensitive resin composition layer, the whole surface exposure was performed by the exposure amount of 500 mJ / cm < ² > using the proximity exposure machine (Ushio Electric make, brand name: UX-1000SM). Then, it was cured by heating at 120 ° C. for 40 minutes and then at 200 ° C. for 60 minutes to obtain a cured film having a thickness of 50 μm. This cured film was immersed in purified water for 24 hours together with the glass plate, and the water absorption was determined from the following formula (a) from the weight change before and after.
Water absorption (%) = (weight of cured film after immersion−weight of cured film before immersion) / (weight of cured film before immersion) × 100 (a)

  As can be seen from Table 2, in the photosensitive resin compositions obtained in Examples 1 to 4, the film loss at the exposed portion was small, and no bleeding or the like was observed. From the above, it was confirmed that the photosensitive resin composition of the present invention can obtain sufficient developability and can perform image formation with high resolution even with a thick film.

It is a schematic cross section which shows an example of the semiconductor package which used the hardening body formed with the photosensitive resin composition of this invention as an interlayer insulation film.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Silicon wafer (substrate), 2 ... Electrode, 3 ... Interlayer insulation film, 4 ... Rewiring, 5 ... Post part, 6 ... Sealing resin, 10 ... Semiconductor package.

Claims (5)

(A) a polyamic acid having a structural unit represented by each of the following general formulas (1), (2) and (3);
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
A photosensitive resin composition comprising:

[In the formulas (1), (2) and (3), Ar ¹ represents a tetracarboxylic dianhydride residue, Ar ² and Ar ³ each independently represent a diamine residue, and R ¹ represents an ethylenic group. A saturated group is shown, and at least one of Ar ¹ and Ar ² has an alkylene group having 5 to 20 carbon atoms in the main chain. ] The photosensitive resin composition of Claim ¹ whose said Ar1 is a tetravalent group represented by following General formula (4).

[In the formula (4), X represents an alkylene group having 5 to 20 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms. M and n each independently represent an integer of 1 to 3, and when m is 2 or more, a plurality of R ² may be the same or different, and when n is 2 or more, a plurality of R ³ are present. May be the same or different. ] Wherein Ar ² is a divalent group represented by the following general formula (5), according to claim 1 or 2 photosensitive resin composition.

[In Formula (5), Z represents a single bond or a divalent organic group, and Y ¹ and Y ² each independently represent an alkylene group having 5 to 20 carbon atoms. ] The photosensitive resin composition according to claim 3, wherein Z is at least one group selected from the group consisting of divalent groups represented by the following general formulas (6), (7) and (8). object.

[In the formulas (6), (7) and (8), R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or carbon. 1 to 3 represent an alkoxy group, q, r and p each independently represent an integer of 1 to 4, and when q is 2 or more, a plurality of R ⁴ may be the same or different, and r When R is 2 or more, a plurality of R ⁵ may be the same or different. When p is 2 or more, a plurality of R ⁶ may be the same or different. ]   A photosensitive element provided with a support body and the layer which consists of a photosensitive resin composition in any one of Claims 1-4 formed on this support body.

Images