JP5758300B2 - Photosensitive resin composition containing polyimide precursor, photosensitive film, coverlay, flexible printed wiring board, and laminate thereof - Google Patents

Description

The present invention relates to a photosensitive resin composition comprising a polyimide precursor having a polyamic acid structure and a polyimide structure as repeating structural units, each having an alkyl ether structure and an aliphatic diamine selectively introduced into the polyimide structure. photosensitive with sexual resin composition film, the photosensitive film obtained cover lay with, and a flexible printed board, and laminates thereof.

  In recent years, a film-like printed circuit board called a flexible printed circuit board (hereinafter also referred to as “FPC”) has gained popularity. This flexible printed circuit board has a structure with a cover lay made of polyimide film on FCCL (Flexible Copper Clad Laminate) that has been subjected to wiring processing, and is mainly used for mobile phones, notebook computers, digital cameras, etc. Used in electronic equipment. Since FPC maintains its function even when it is bent, it has become an indispensable material for reducing the size and weight of electronic devices. In particular, in recent years, electronic devices represented by notebook computers have been reduced in size and weight, and by adopting FPC for such products, the size and weight of the electronic devices are reduced, the product cost is reduced, and the design is reduced. Contributes to the simplification of

  Development of photosensitive coverlays has been vigorously performed for fine processing by lithography for miniaturization and thinning of FPC. Among these, a photosensitive cover lay using a polyimide precursor is expected as an excellent cover lay from the viewpoint of bending resistance derived from polyimide, heat resistance, and electrical insulation.

  Further, conventional screen printing has problems such as a solvent removal process and double-side processing, and the like, and the resolution of screen printing is lowered. For this reason, it is desired that the photosensitive resin composition be formed into a dry film from the viewpoint of the industrial process and the resolution.

  As a photosensitive resin composition for solving these problems, a photosensitive resin composition containing a polyimide precursor having both a polyamic acid structure and a polyimide structure, a negative photosensitive resin composition in which an exposed portion is insoluble ( Patent Document 1) and a photosensitive resin composition (Patent Document 2) containing a polyimide precursor having a polyamic acid structure have been proposed. However, in the photosensitive resin composition described in Patent Document 1, the aliphatic diamine constituting the polyimide precursor is present in the polyamic acid structure, and in the photosensitive resin composition described in Patent Document 2, the polyimide precursor The body has a polyamic acid structure. For this reason, the molecular weight fall of the varnish which dissolved the photosensitive resin composition in the solvent becomes large. Furthermore, the decrease in the molecular weight in the baking (heat drying) step in the production of the dry film is also increased, and there is a problem that the photosensitive layer is cracked when the photosensitive dry film that can reduce the toughness of the film is folded. . Furthermore, when the pattern is formed by lithography due to the decrease in the molecular weight of the polyimide precursor, the development performance such as the development time is not stable, the remaining film ratio is decreased, and the pattern shape is distorted in development using an aqueous alkaline solution. Tended to decrease.

  Further, in the step of converting the polyimide precursor to polyimide, the FPC may be warped due to stress resulting from solvent removal or a ring closure reaction accompanying imidization of the polyimide precursor. When warpage occurs in the FPC, problems such as poor adhesion between the FCCL and the coverlay and an increase in driving power of an electronic device equipped with the FPC arise. For this reason, it is required to improve the warpage of the FPC having a coverlay on the copper wiring.

JP 2006-321924 A JP 05-158237 A

  The present invention has been made in view of the above points. When the film is bent, the photosensitive layer is not cracked, developability is good, and when used for a flexible printed circuit board (FPC), firing is performed. Use of a polyimide precursor suitable as an FPC coverlay with less warping of subsequent FPC, a photosensitive resin composition containing the polyimide precursor, a photosensitive film using the photosensitive resin composition, and the photosensitive film It aims at providing the flexible printed circuit board obtained by this, and its laminated body.

  As a result of intensive studies, the present inventors have determined that a polyimide precursor having a polyamic acid structure and a polyimide structure as repeating structural units and selectively introducing an aliphatic diamine having a specific alkyl ether structure into the polyimide structure, A photosensitive resin composition using a polyimide precursor, a photosensitive film using the photosensitive resin composition, a flexible printed board obtained using the photosensitive film, and a laminate thereof solve the above problems. As a result, the present invention has been completed. That is, the present invention is as follows.

（式（１）及び式（５）中、Ｒ _１ 、Ｒ _２ 、Ｒ _４ 、Ｒ _５ 、Ｒ _７ 、Ｒ _８ 、Ｒ _１０ 、Ｒ _１１ 、Ｒ _１３ 、Ｒ _１４ はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていてもよい。式（１）及び式（５）中、Ｒ _３ 、Ｒ _６ 、Ｒ _９ 、Ｒ _１２ 、Ｒ _１５ は、炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。式（１）及び式（２）中、Ｒ _１６ は式（３）又は式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、式（２）及び式（８）中、Ｒ _１７ は、炭素数１〜炭素数９０の２価の有機基を表す。式（３）中、Ｘは、単結合、カルボニル基又はスルホニル基を表し、式（４）中、Ｙは、芳香環を有する２価の有機基又は炭素数１〜炭素数２０の２価の有機基を表す。ａは１以上２０以下の整数を表す。） The photosensitive resin composition of the present invention contains (A) a polyimide precursor and (B) a photosensitizer, and the photosensitizer (B) contains two or more photopolymerizable unsaturated double bonds. The (A) polyimide precursor includes a polyimide structure represented by the following general formula (1), and the following general formula (2). And a tetracarboxylic dianhydride constituting the polyimide precursor is represented by the following general formula (3) and the following general formula (4). comprising comprising one or more tetracarboxylic dianhydrides that will be selected from the group, see containing a diamine diamine constituting the polyimide structure represented by the following general formula (5), the table the following general formula (2) Polyamic acid The structure includes a diamine represented by the following general formula (8), and the diamine represented by the following general formula (8) is 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4 -Aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoro (Romethyl) -4,4′-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis ( 4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy ] Ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) Biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, trimethylene-bis (4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5- Diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 1,3-bis (4- Wherein the amino phenoxy is any one of sheet benzene).

(In Formula (1) and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In formula (1) and formula (2), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and in the formula (2) and the formula (8), R ₁₇ has 1 carbon atom. -Represents a divalent organic group having 90 carbon atoms, wherein in formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in formula (4), Y represents an aromatic ring 2 Is .a representing the organic group or a divalent organic group with carbon number from 1 to 20 carbon atoms represents an integer of 1 to 20.)

In the photosensitive resin composition of the present invention, a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, a compound having two double bonds, and three or more double bonds It is preferable to contain both the compound which has .

（式（１）及び式（５）中、Ｒ _１ 、Ｒ _２ 、Ｒ _４ 、Ｒ _５ 、Ｒ _７ 、Ｒ _８ 、Ｒ _１０ 、Ｒ _１１ 、Ｒ _１３ 、Ｒ _１４ はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていてもよい。式（１）及び式（５）中、Ｒ _３ 、Ｒ _６ 、Ｒ _９ 、Ｒ _１２ 、Ｒ _１５ は、炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。式（１）及び式（２）中、Ｒ _１６ は式（３）又は式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、式（２）及び式（８）中、Ｒ _１７ は、炭素数１〜炭素数９０の２価の有機基を表す。式（３）中、Ｘは、単結合、カルボニル基又はスルホニル基を表し、式（４）中、Ｙは、芳香環を有する２価の有機基又は炭素数１〜炭素数２０の２価の有機基を表す。ａは１以上２０以下の整数を表す。） The photosensitive resin composition of the present invention contains (A) a polyimide precursor and (B) a photosensitizer, and the (B) photosensitizer contains a quinonediazide compound, and the (A) polyimide precursor is , A polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively. The carboxylic acid dianhydride contains one or more tetracarboxylic dianhydrides selected from the group consisting of the following general formula (3) and the following general formula (4), and the diamine constituting the polyimide structure is The polyamic acid structure represented by the following general formula (2) contains the diamine represented by the following general formula (8), and includes the diamine represented by the following general formula (8). Said Zia Min is 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, , 3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 3,3 ′ -Diaminodiphenyl sulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiop Ene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1, 3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5- Amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-a Nophenoxyphenyl) propane, trimethylene-bis (4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis [4- (4-aminophenoxy) Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-aminomethyl-3,5 , 5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 1,3-bis It is any one of (4-aminophenoxybenzene).

(In Formula (1) and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In formula (1) and formula (2), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and in the formula (2) and the formula (8), R ₁₇ has 1 carbon atom. -Represents a divalent organic group having 90 carbon atoms, wherein in formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in formula (4), Y represents an aromatic ring 2 Is .a representing the organic group or a divalent organic group with carbon number from 1 to 20 carbon atoms represents an integer of 1 to 20.)

（式（１）及び式（５）中、Ｒ _１ 、Ｒ _２ 、Ｒ _４ 、Ｒ _５ 、Ｒ _７ 、Ｒ _８ 、Ｒ _１０ 、Ｒ _１１ 、Ｒ _１３ 、Ｒ _１４ はそれぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていてもよい。式（１）及び式（５）中、Ｒ _３ 、Ｒ _６ 、Ｒ _９ 、Ｒ _１２ 、Ｒ _１５ は、炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。式（１）及び式（２）中、Ｒ _１６ は式（３）又は式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、式（２）及び式（８）中、Ｒ _１７ は、炭素数１〜炭素数９０の２価の有機基を表す。式（３）中、Ｘは、単結合、カルボニル基又はスルホニル基を表し、式（４）中、Ｙは、芳香環を有する２価の有機基又は炭素数１〜炭素数２０の２価の有機基を表す。ａは１以上２０以下の整数を表す。）

（式（７）中、Ｒ _１９ は、−Ａｒ−Ｚ−Ａｒ−又は−Ａｒ−Ｚ−Ａｒ−Ｚ−Ａｒ−であり、ＺはＯ又はＳＯ _２ である。またＲ _２０ は、炭素数２〜炭素数１０のアルキル基である。） In the photosensitive resin composition of the present invention, the reactive resin composition contains (A) a polyimide precursor and (B) a photosensitizer, and (D) a reactive compound having reactivity with the polyimide precursor, and is reactive. The compound is represented by the following formula (7), and the (A) polyimide precursor repeats a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2), respectively. It is a polyimide precursor which has as a structural unit, Comprising: The tetracarboxylic dianhydride which comprises this polyimide precursor is one or more selected from the group which consists of following General formula (3) and following General formula (4) The diamine which comprises tetracarboxylic dianhydride and which comprises this polyimide structure contains the diamine represented by the following general formula (5), and the polyamic acid structure represented by the following general formula (2) has the following general formula (8 ) The diamine represented by the following general formula (8) includes 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5- Bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4 ′ -Diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4'- Diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-dia Minobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis (4-aminophenyl) sulfide, 4 , 4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-bis 3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, trimethylene-bis (4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl- 4-aminobenzoate, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexa Fluoropropane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′- Dihydroxy-4,4′-diaminobiphenyl, 1,3-bis (4-aminophenoxybenzene) It is preferably any one.

(In Formula (1) and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In formula (1) and formula (2), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and in the formula (2) and the formula (8), R ₁₇ has 1 carbon atom. -Represents a divalent organic group having 90 carbon atoms, wherein in formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in formula (4), Y represents an aromatic ring 2 Is .a representing the organic group or a divalent organic group with carbon number from 1 to 20 carbon atoms represents an integer of 1 to 20.)

(In the formula _{(7), R 19} is -Ar-Z-Ar- or -Ar-Z-Ar-Z- Ar- in and, Z is O or SO _2. The _{R 20} is 2 carbon atoms To an alkyl group having 10 carbon atoms.

In the photosensitive resin composition of the present invention preferably contains a reactive compound having reactivity with one or more resins selected from the group consisting of (D) a thermosetting resin and a polyimide precursor.

In the photosensitive resin composition of this invention, it is preferable that (E) phosphorus compound is included .

In the photosensitive resin composition of this invention, it is preferable that (E) phosphorus compound has one or more structures selected from the group which consists of a phosphate ester structure and a phosphazene structure .

（式（５−１）中、Ｒ _１８ は、Ｃ _２ Ｈ _４ 又はＣ _４ Ｈ _８ であり、ｍ、ｎ、ｐは、それぞれ独立して０以上４０以下の整数であり、１２≦（ｍ＋ｎ＋ｐ）≦４０を満たす。） In the photosensitive resin composition of the present invention, the diamine represented by the general formula (5) is preferably a diamine represented by the following general formula (5-1) .

(In Formula (5-1), R ₁₈ is C ₂ H ₄ or C ₄ H ₈ , m, n, and p are each independently an integer of 0 or more and 40 or less, and 12 ≦ (m + n + p) ≦ 40 is satisfied.)

（式（６）中、Ｒ _１ 、Ｒ _２ 、Ｒ _４ 、Ｒ _５ 、Ｒ _７ 、Ｒ _８ 、Ｒ _１０ 、Ｒ _１１ 、Ｒ _１３ 、Ｒ _１４ は、それぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていてもよい。Ｒ _３ 、Ｒ _６ 、Ｒ _９ 、Ｒ _１２ 、Ｒ _１５ は、炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ _１６ は、前記一般式（３）又は前記一般式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ _１７ は、炭素数１〜炭素数９０の２価の有機基を表す。Ｘは、単結合、カルボニル基、スルホニル基を表し、Ｙは、芳香環を含む２価の有機基又は炭素数１〜炭素数２０の脂肪族の２価の有機基を表す。ａは１以上２０以下の整数を表す。Ａ、Ｂ、Ｃは各単位のｍｏｌ％を表し、０＜Ａ＜１００、０＜Ｂ＜１００、０＜Ｃ＜１００、０．０５≦Ｃ／（Ａ＋Ｂ＋Ｃ）≦０．９５を満たす。） In the photosensitive resin composition of the present invention, the (A) polyimide precursor is preferably represented by the following general formula (6) .

(In the formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon number 1 to carbon. Represents a monovalent organic group having the number 20, and may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ are each a tetravalent organic having 1 to 20 carbon atoms. And m, n and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4). R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms, X represents a single bond, a carbonyl group, or a sulfonyl group, and Y represents an aromatic ring. Represents a divalent organic group containing 1 or an aliphatic divalent organic group having 1 to 20 carbon atoms, and a represents an integer of 1 to 20. .A, B, C represents the mol% of each unit, satisfy 0 <A <100,0 <B < 100,0 <C <100,0.05 ≦ C / (A + B + C) ≦ 0.95.)

（式（６−１）中、Ｒ _１６ は、前記一般式（３）又は前記一般式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ _１７ は、炭素数１〜炭素数９０の２価の有機基を表し、Ｒ _１８ は、Ｃ _２ Ｈ _４ 又はＣ _４ Ｈ _８ であり、ｍ、ｎ、ｐはそれぞれ独立して０以上４０以下の整数であり１２≦（ｍ＋ｎ＋ｐ）≦４０である。） In the optical resin composition of the present invention, the (A) polyimide precursor is preferably represented by the following general formula (6-1).

(In the formula (6-1), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4), and R ₁₇ is Represents a divalent organic group having 1 to 90 carbon atoms, R ₁₈ is C ₂ H ₄ or C ₄ H ₈ , and m, n, and p are each independently an integer of 0 to 40. Yes 12 ≦ (m + n + p) ≦ 40)

  The photosensitive film of this invention is characterized by including a support film layer and the said photosensitive resin composition provided on this support film.

  In the photosensitive film of this invention, it is preferable to have a carrier film on one side.

  The photosensitive film of the present invention preferably includes a cover film.

  The coverlay of the present invention is characterized by having a structure obtained by imidizing the photosensitive resin composition.

  The flexible printed wiring board of the present invention has a structure in which the photosensitive resin composition is imidized.

  The laminated body of this invention was provided with the said coverlay and the copper clad laminated board.

  According to the present invention, there is no cracking of the photosensitive layer even when it is folded into a film, the developability is good, and the FPC warpage of the FPC after firing is small when used for a flexible printed circuit (FPC). A polyimide precursor suitable as a coverlay, a photosensitive resin composition containing the polyimide precursor, a photosensitive film using the photosensitive resin composition, a flexible printed circuit board obtained using the photosensitive film, and its A laminate can be provided.

It is a figure which shows the infrared absorption spectrum of the thermal base generator 1 which concerns on the synthesis example 1 of the Example of this invention. It is a figure which shows the infrared absorption spectrum of the polyimide precursor film which concerns on Example 1 of the Example of this invention. It is a figure which shows the infrared absorption spectrum of the polyimide precursor film which concerns on Example 4 of the Example of this invention. It is a figure which shows the infrared absorption spectrum of the photosensitive resin composition which concerns on Example 11 of the Example of this invention.

The present invention will be specifically described below.
(A) Polyimide precursor The polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively. The tetracarboxylic dianhydride constituting the polyimide precursor comprises at least one tetracarboxylic dianhydride selected from the group consisting of the following general formula (3) and the following general formula (4), The diamine constituting the polyimide structure is the following general formula (5).

（式（１）、式（２）、及び式（５）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４は、それぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていてもよい。式（１）及び式（５）中、Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。式（２）中、Ｒ_１６は、式（３）又は式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ_１７は、炭素数１〜炭素数９０の２価の有機基を表す。式（３）中、Ｘは、単結合、カルボニル基、スルホニル基を表し、式（４）中、Ｙは、芳香環を有する２価の有機基又は炭素数１〜炭素数２０の２価の有機基を表す。ａは１以上２０以下の整数を表す。）

(In Formula (1), Formula (2), and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are respectively Independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ each represent a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In the formula (2), R ₁₆ represents a tetravalent organic group derived from a tetracarboxylic dianhydride represented by formula (3) or formula (4), and R ₁₇ is a divalent organic group having 1 to 90 carbon atoms. In the formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in the formula (4), Y represents a divalent organic group having an aromatic ring or 1 to 1 carbon atoms. .a representing a divalent organic group of prime 20 represents an integer of 1 to 20.)

  The polyimide precursor according to the present invention is obtained by the following synthesis method. First, a tetracarboxylic dianhydride represented by at least one selected from the group consisting of the general formula (3) and the general formula (4), and an aliphatic diamine represented by the general formula (5) And, after obtaining a polyimide by polymerization and cyclization, tetracarboxylic dianhydride represented by at least one selected from the group consisting of the general formula (3) and the general formula (4), A polyimide precursor can be obtained by polymerizing a diamine represented by the following general formula (8).

（式（８）中、Ｒ_１７は、炭素数１〜炭素数９０の２価の有機基を表す。）

(In the formula (8), R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms.)

  The obtained polyimide precursor preferably has a structure represented by the following general formula (6).

（式（６）中、Ｒ_１、Ｒ_２、Ｒ_４、Ｒ_５、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、Ｒ_１３、Ｒ_１４は、それぞれ独立して水素原子又は炭素数１〜炭素数２０の１価の有機基を表し、同じであっても異なっていてもよい。Ｒ_３、Ｒ_６、Ｒ_９、Ｒ_１２、Ｒ_１５は、炭素数１〜炭素数２０の４価の有機基を表し、ｍ、ｎ、ｐはそれぞれ独立して０以上１００以下の整数を表す。Ｒ_１６は、上記一般式（３）又は上記一般式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ_１７は、炭素数１〜炭素数９０の２価の有機基を表す。Ｘは、単結合、カルボニル基、スルホニル基を表し、Ｙは、芳香環を含む２価の有機基又は炭素数１〜炭素数２０の脂肪族の２価の有機基を表す。ａは１以上２０以下の整数を表す。Ａ、Ｂ、Ｃは各単位のｍｏｌ％を表し、０＜Ａ＜１００、０＜Ｂ＜１００、０＜Ｃ＜１００、０．０５≦Ｃ／（Ａ＋Ｂ＋Ｃ）≦０．９５を満たす。）

(In the formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon number 1 to carbon. Represents a monovalent organic group having the number 20, and may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ are each a tetravalent organic having 1 to 20 carbon atoms. And m, n and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4). R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms, X represents a single bond, a carbonyl group, or a sulfonyl group, and Y represents an aromatic ring. Represents a divalent organic group containing 1 or an aliphatic divalent organic group having 1 to 20 carbon atoms, and a represents an integer of 1 to 20. .A, B, C represents the mol% of each unit, satisfy 0 <A <100,0 <B <100,0 <C <100,0.05 ≦ C / (A + B + C) ≦ 0.95.)

  Examples of the tetracarboxylic dianhydride represented by the general formula (3) include biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as BPDA), benzophenone-3, Examples thereof include 3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter abbreviated as BTDA), diphenylsulfone-3,3 ′, 4,4′-tetracarboxylic dianhydride, and the like.

  Examples of the tetracarboxylic dianhydride represented by the general formula (4) include ethylene glycol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as TMEG), p-phenylene bis (trimellitic acid monoanhydride). Ester acid anhydride), p-biphenylenebis (trimellitic acid monoester acid anhydride), m-phenylenebis (trimellitic acid monoester acid anhydride), o-phenylenebis (trimellitic acid monoester acid anhydride) , Pentanediol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as 5-BTA), decanediol bis (trimellitic acid monoester acid anhydride), and the like.

  The diamine represented by the general formula (5) is not limited as long as it has the structure represented by the general formula (5), but may be 1,8-diamino-3,6-dioxyoctane or the like. Polyoxyethylenediamine compounds, polyoxyalkylenediamine compounds such as Huntsman's Jeffermine EDR-148 and EDR-176, polyoxypropylenediamine compounds such as Jeffamine D-230, D-400, D-2000, and D-4000, Examples thereof include compounds having different oxyalkylene groups such as HK-511, ED-600, ED-900, ED-2003, and XTJ-542. The skeleton having these oxyalkylene groups can reduce the warpage of FPC after baking of the polyimide.

  In the above formula (6), m, n, and p are each independently an integer of 0 or more and 100 or less. m + n + p> 5 is preferable, and m + n + p> 10 is more preferable. The polyimide precursor according to the present invention has a polyimide structure and a polyamic acid structure as repeating structural units, respectively. By introducing the diamine represented by the general formula (5) into the polyimide structure, the polyimide precursor is obtained. The molecular weight of the varnish and film is stabilized. When the diamine of the general formula (5) is introduced into the polyamic acid structure, the basicity of the aliphatic diamine is high, and the depolymerization of the polyamic acid proceeds and the molecular weight is significantly reduced as compared with the conventional polyamic acid. By introducing the diamine represented by the general formula (5) into the polyimide structure, the molecular weight is stabilized without being affected by the basicity of the aliphatic diamine.

  Furthermore, from the viewpoint of reducing the warpage of the film, among the diamines represented by the general formula (5), diamines represented by the following formula (5-1) are more preferable.

（式（５−１）中、Ｒ_１８は、Ｃ_２Ｈ_４又はＣ_４Ｈ_８であり、ｍ、ｎ、ｐはそれぞれ独立して０以上４０以下の整数であり、１２≦（ｍ＋ｎ＋ｐ）≦４０を満たす。）

(In the formula (5-1), R ₁₈ is C ₂ H ₄ or C ₄ H ₈ , m, n, and p are each independently an integer of 0 or more and 40 or less, and 12 ≦ (m + n + p) ≦ 40.)

From the viewpoint of developability and low water absorption, R ₁₈ is preferably C ₂ H ₄ or C ₄ H ₈ . Moreover, it is preferable to satisfy | fill 12 <= (m + n + p) from the point of the melt | dissolution rate in developability, and it is (m + n + p) <= 40 from the point which suppresses the tackability (adhesiveness) of a film and expresses a flame retardance. preferable. Furthermore, among the above general formula (5-1), a diamine represented by any one of the following general formula (5-2), the following general formula (5-3), or the following general formula (5-4) is particularly preferable. . Formula (5-2) corresponds to Jeffamine D-2000, Formula (5-3) corresponds to Jeffamine ED-900, and Formula (5-4) represents Jeffamine XTJ-542 ( Both correspond to Huntsman's).

（式（５−３）及び式（５−４）中、Ｆ及びＧは、Ｆ＋Ｇ＝６を満たす。）

(In Formula (5-3) and Formula (5-4), F and G satisfy F + G = 6)

  Examples of the diamine represented by the general formula (8) include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as DAS), 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4 '-Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoro Til) -4,4′-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone, 4,4′-bis ( 4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy ] Ethane, 9,9-bis (4-aminophenyl) fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4 -Bis (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter abbreviated as BAPP), trimethylene-bis ( 4-aminobenzoate) (hereinafter abbreviated as TMAB), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, bis [4- (4-aminophenoxy) phenyl] Sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino-3-aminomethyl-3,5,5 -Trimethylcyclohexane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,5 -Diaminobenzoic acid, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 1,3-bis (4-aminophenoxybenzene) and the like. Among these, DAS, APB, BAPP, and TMAB are preferable from the viewpoint of low Tg of the polyimide precursor and developability. Some of these diamines can also be used as a diamine for polyimide synthesis.

（式（６−１）中、Ｒ１６は、上記一般式（３）又は上記一般式（４）で表されるテトラカルボン酸二無水物に由来する４価の有機基を表し、Ｒ１７は、炭素数１〜炭素数９０の２価の有機基を表し、Ｒ１８は、Ｃ２Ｈ４又はＣ４Ｈ８であり、ｍ、ｎ、ｐはそれぞれ独立して０以上４０以下の整数であり１２≦（ｍ＋ｎ＋ｐ）≦４０である。） Here, the polyimide precursor is effective even when used as a negative photosensitive resin composition or as a positive photosensitive resin composition. The polyimide precursor is not limited as long as it has the structure represented by the general formula (1) and the general formula (2) as a structural unit. However, from the viewpoint of developability, the general formula (6) is further used. ) Is preferably a block copolymer having a polyimide structure and a polyamic acid structure represented by repeating structural units, respectively, and the polyimide structure and the polyamic acid structure represented by the following general formula (6-1) are each repeated. More preferably, it is a block copolymer as a structural unit.

(In the formula (6-1), R16 represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4), and R17 represents carbon. Represents a divalent organic group having 1 to 90 carbon atoms, R18 is C2H4 or C4H8, m, n, and p are each independently an integer of 0 to 40 and 12 ≦ (m + n + p) ≦ 40 is there.)

  Among the polyimide precursors shown in the general formula (6) including the polyimide precursor shown in the general formula (6) and the block copolymer shown in the general formula (6-1), from the viewpoint of developability, 0. A polyimide precursor satisfying 1 ≦ C / (A + B + C) ≦ 0.9 is preferable, a polyimide precursor satisfying 0.2 ≦ C / (A + B + C) ≦ 0.8 is more preferable, and 0.5 ≦ C / (A + B + C). A polyimide precursor satisfying ≦ 0.75 is most preferred.

  The tetracarboxylic dianhydride may contain a tetracarboxylic dianhydride other than the above general formula (3) and the above general formula (4) as long as the performance is not adversely affected.

  Other tetracarboxylic dianhydrides include pyromellitic anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 3,3′-oxydiphthalic dianhydride, 4,4′-oxydiphthalic dianhydride 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, meta-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5 6-tetracarboxylic dianhydride, cyclobutane-1,2,3,4-tetracarboxylic dianhydride, 1-carboxymethyl-2,3,5-cyclopentatricarboxylic acid-2,6: 3,5- Dianhydro 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydrofuryl)- Examples include 3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.

  The content of other tetracarboxylic dianhydrides is 50 parts by mass or less when the tetracarboxylic dianhydride represented by the general formula (3) and the general formula (4) is 100 parts by mass. .

  The end of the main chain of the polyimide precursor is not particularly limited as long as it does not affect the performance. A terminal derived from an acid dianhydride or a diamine used for producing a polyimide precursor may be used, or the terminal may be sealed with another acid anhydride, an amine compound, or the like.

  The polyimide precursor preferably has a weight average molecular weight of 1,000 or more and 1,000,000 or less. Here, the weight average molecular weight refers to a molecular weight measured by gel permeation chromatography (GPC) using polystyrene having a known weight average molecular weight as a standard. The weight average molecular weight is preferably 1000 or more from the viewpoint of the strength of the polyimide film, and is preferably 1000000 or less from the viewpoint of the viscosity and moldability of the polyimide-containing resin composition. The weight average molecular weight is more preferably from 5,000 to 500,000, particularly preferably from 10,000 to 300,000, and most preferably from 25,000 to 50,000.

  A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units, respectively, is a step of reacting acid dianhydride and diamine in a non-equal molar amount to synthesize a first-stage polyimide site (step 1), followed by It can be produced by a step of synthesizing the second stage polyamic acid (step 2). Hereinafter, each process will be described.

(Process 1)
The process of synthesizing the first-stage polyimide site will be described. The step of synthesizing the first-stage polyimide site is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, diamine is dissolved and / or dispersed in a polymerization solvent, and acid dianhydride powder is added thereto. Then, a solvent that is azeotroped with water is added, and the mixture is heated and stirred for 0.5 hours to 96 hours, preferably 0.5 hours to 30 hours, while removing by-product water azeotropically using a mechanical stirrer. In this case, the monomer concentration is 0.5% by mass or more and 95% by mass or less, preferably 1% by mass or more and 90% by mass or less.

  In the synthesis of the polyimide site, the polyimide site can be synthesized either by adding a known imidization catalyst or without a catalyst. The imidation catalyst is not particularly limited, but acid anhydrides such as acetic anhydride, lactones such as γ-valerolactone, γ-butyrolactone, γ-tetronic acid, γ-phthalide, γ-coumarin, and γ-phthalide acid. Examples thereof include compounds, tertiary amines such as pyridine, quinoline, N-methylmorpholine, and triethylamine. Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. Among these, a mixed system of γ-valerolactone and pyridine and a non-catalyst are particularly preferable from the viewpoint of high reactivity and influence on the next reaction.

  The amount of the imidization catalyst added is preferably 50 parts by mass or less, and more preferably 30 parts by mass or less when the polyamic acid is 100 parts by mass.

  The reaction solvent used in the synthesis of the polyimide moiety includes 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether. Ether compounds of: ketone compounds having 2 to 6 carbon atoms such as acetone and methyl ethyl ketone; saturated compounds having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane and decalin Hydrocarbon compounds; aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as benzene, toluene, xylene, mesitylene, tetralin; methyl acetate, ethyl acetate Ester compounds such as γ-butyrolactone and methyl benzoate having 3 to 12 carbon atoms; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing compounds having 2 to 10 carbon atoms; sulfur-containing compounds such as dimethyl sulfoxide. These may be one kind or a mixture of two or more kinds as required. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon atoms having 2 to carbon atoms. A nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The synthesis of the polyimide site is preferably carried out at a reaction temperature of 15 ° C. or higher and 250 ° C. or lower. If it is 15 degreeC or more, reaction will be started, and if it is 250 degrees C or less, there will be no deactivation of a catalyst. Preferably they are 20 degreeC or more and 220 degrees C or less, More preferably, they are 20 degreeC or more and 200 degrees C or less.

  The time required for the reaction for synthesizing the polyimide moiety varies depending on the purpose or reaction conditions, but is usually within 96 hours, particularly preferably in the range of 30 minutes to 30 hours.

(Process 2)
Next, the process for synthesizing the second stage polyamic acid moiety will be described. The synthesis of the polyamic acid moiety in the second stage can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and adding diamine and / or acid dianhydride for polymerization.

  The polymerization temperature in the synthesis of the second stage polyamic acid is preferably 0 ° C. or higher and 250 ° C. or lower, more preferably 0 ° C. or higher and 100 ° C. or lower, and particularly preferably 0 ° C. or higher and 80 ° C. or lower.

  The time required for the synthesis reaction of the polyamic acid varies depending on the purpose or reaction conditions, but is usually within 96 hours, and particularly preferably 30 minutes to 30 hours.

  As the reaction solvent, the same solvent used for the synthesis of the polyimide moiety in Step 1 can be used. In that case, the reaction solution of step 1 can be used as it is. Moreover, you may use the solvent different from what was used for the synthesis | combination of a polyimide site | part.

  Examples of such solvents include ether compounds having 2 to 9 carbon atoms such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; acetone, methyl ethyl ketone, and the like. A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms, such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, decalin; benzene, toluene, xylene Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as mesitylene and tetralin; methyl acetate, ethyl acetate, γ-butyrolactone, benzoic acid Ester compounds having 3 to 12 carbon atoms such as chill; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethylformamide N, N-dimethylacetamide, N-methyl-2-pyrrolidone and other nitrogen-containing compounds having 2 to 10 carbon atoms; sulfur-containing compounds such as dimethyl sulfoxide.

  These may be one kind or a mixture of two or more kinds as required. Particularly preferable solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 12 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and carbon atoms having 2 to carbon atoms. A nitrogen-containing compound of several tens or less is mentioned. These can be arbitrarily selected in consideration of industrial productivity and influence on the next reaction.

  The polyimide precursor after the production may be used as it is dissolved in the reaction solvent, or may be recovered and purified by the following method.

  Recovery of the polyimide precursor after completion of production can be carried out by distilling off the solvent in the reaction solution under reduced pressure.

  Examples of the method for purifying the polyimide precursor include a method of removing insoluble acid dianhydride and diamine in the reaction solution by vacuum filtration, pressure filtration, or the like. In addition, a so-called reprecipitation purification method in which the reaction solution is precipitated by adding it to a poor solvent can be carried out. Further, when a highly pure polyimide precursor is required, an extraction method by a carbon dioxide supercritical method is also possible.

(B) Photosensitive agent The photosensitive resin composition according to the present invention contains the polyimide precursor and a photosensitizer. A photosensitizer is a compound having a property that its structure is changed by light irradiation and its solubility in a solvent is changed. Examples of such a compound include a so-called positive type in which the light irradiation site is dissolved and a so-called negative type in which the light irradiation site is insoluble.

  Examples of the negative type photosensitizer include a combination of (B-1) a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds and (C) a photopolymerization initiator.

(B-1) (Meth) acrylate compound having two or more photopolymerizable unsaturated double bonds

Examples of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds include tricyclodecane dimethylol diacrylate, ethylene oxide (EO) modified bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A diacrylate, 1,6-hexanediol (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi ( (Meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylo Rupuropantori (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, beta-hydroxypropyl-beta '- (acryloyl O carboxymethyl) -Propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri / tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, urethane di (meth) a Chlorate. Among these, EO-modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, and pentaerythritol tri / tetra (meth) acrylate are preferable from the viewpoint of reducing warpage after firing. A combination of a compound having two double bonds and a compound having three or more double bonds is preferred. The amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is from 5 parts by weight to 60 parts by weight from the viewpoint of developability when the amount of the polyimide precursor is 100 parts by weight. Is preferably 10 parts by mass or more and 40 parts by mass or less.

(C) Photopolymerization initiator Examples of the photopolymerization initiator include benzyldimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyldipropyl ketals, benzyldiphenyl ketals, and benzoin. Methyl ethers, benzoin ethyl ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-isopropylthioxanthone, 2-fluorothioxanthone, 4-fluorothioxanthone 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, benzophenone, 4,4′-bis (dimethylamino) benzophenone [Michler's ketone], 4,4′- Aromatic ketone compounds such as su (diethylamino) benzophenone, 2,2-dimethoxy-2-phenylacetophenone, triarylimidazole dimers such as N-phenylglycine and lophine dimer, acridine compounds such as 9-phenylacridine, Oxime ester compounds such as α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, N-aryl-α-amino acid, p-dimethylaminobenzoic acid, p-dimethylamino Benzoic acid, p-diethylaminobenzoic acid, p-diisopropylaminobenzoic acid, p-benzoic acid ester, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4-[(2-hydroxy-2-methyl- Α-hydroxyalkylphenones such as propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 Α-Aminoalkylphenones such as 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethyl Acylphosphine oxy, such as benzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Sides, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 And oxime esters such as -yl] -1- (O-acetyloxime). Among these, oxime esters are preferable from the viewpoint of sensitivity.

  When the amount of the polyimide precursor is 100 parts by mass, the amount of the photopolymerization initiator is preferably 0.01 parts by mass or more and 40 parts by mass or less from the viewpoint of sensitivity and resolution. 0.5 parts by mass or more and 35 parts by mass or less are more preferable.

(B-2) Quinonediazide compound Examples of the compound exhibiting positive photosensitivity include compounds containing a quinonediazide structure, aromatic diazonium salt compounds, and compounds having an azide structure. From the viewpoint of solubility contrast, a compound containing a quinonediazide structure is preferred.

  Examples of the compound containing a quinonediazide structure include 1,2-benzoquinonediazidesulfonic acid esters, 1,2-benzoquinonediazidesulfonic acid amides, 1,2-naphthoquinonediazidesulfonic acid esters, 1,2-naphthoquinonediazidesulfonic acid. Amides are mentioned. Specifically, for example, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfone Acid esters, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc. 1,2-naphthoquinone diazide sulfonic acid esters of trihydroxybenzophenones; 2,2 ′, 4,4′-tetrahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid ester, 2,2 ′, 4, 4'-tetrahydroxybenzophenone-1,2-naphthoquinone Diazide-5-sulfonic acid ester, 2,2 ′, 3 ′, 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 3 ′, 4-tetrahydroxybenzophenone-1 , 2-Naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2 ′, 3,4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ′, 3,4-tetra Hydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2, , 4,4′-Tetrahydroxy-3′-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone-1,2- 1,2-naphthoquinone diazide sulfonic acid esters of tetrahydroxybenzophenones such as naphthoquinone diazide-5-sulfonic acid ester; 2,2 ′, 3,4,6′-pentahydroxybenzophenone-1,2-naphthoquinone diazide-4 -1,2-naphthoquinone diazide sulfonic acid esters of pentahydroxybenzophenones such as sulfonic acid ester, 2,2 ', 3,4,6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester 2,3 ', 4,4', 6,5'-hex Hydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3 ′, 4,4 ′, 5 ′, 6-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3, 3 ′, 4,4 ′, 5,5′-Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3 ′, 4,4 ′, 5,5′-hexahydroxybenzophenone-1 1,2-naphthoquinone diazide sulfonic acid esters of hexahydroxybenzophenones such as 1,2-naphthoquinone diazide-5-sulfonic acid ester; bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinone diazide-4-sulfone Acid ester, bis (2,4-dihydroxyphenyl) methane-1,2- Naphthoquinonediazide-5-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfone Acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2- Naphthoquinonediazide-5-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2′-bis (2, , 4-Trihydroxyphenyl) propane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2′-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5 Sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris ( 2,5-Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 ′ [1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4- Hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide- 5-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,5 ′, 6,6 ′, 7,7′-hexanol-1,2-naphtho Quinonediazide-4-sulfonic acid ester, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5,5 ′, 6,6 ′, 7,7′-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfone 1,2-naphtho of (polyhydroxyphenyl) alkanes such as acid esters, 2,2,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonate And quinonediazide sulfonic acid esters. From the viewpoint of dissolution inhibiting ability, 1,2-naphthoquinone diazide sulfonic acid esters are preferable, 1,2-naphthoquinone diazide-4-sulfonic acid esters, and 1,2-naphthoquinone diazide-5-sulfonic acid esters are photosensitive. More preferable from the viewpoint of contrast. Among these, a compound represented by the following general formula (9) is particularly preferable.

（式（９）中、Ｑは、式（１０）で表される構造又は水素原子である。）

(In Formula (9), Q is a structure or a hydrogen atom represented by Formula (10).)

  As a photosensitizer, compound b used in Examples described later has a structure in which 2.9 of the three Qs in the general formula (9) are represented by the general formula (10) on average. Point to.

  The amount of the positive photosensitive agent in the photosensitive resin composition is preferably 1 part by mass or more and 50 parts by mass or less, more preferably from the viewpoint of photosensitive contrast, when the amount of the polyimide precursor is 100 parts by mass. 5 parts by mass or more and 30 parts by mass or less. If it is 1 mass part or more, since there exists a tendency for dissolution suppression of an unexposed part to be enough, it is preferable. If it is 50 mass parts or less, since it exists in the tendency for a sensitivity to be high enough, it is preferable.

(D) A compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor In order to improve the toughness, solvent resistance, and heat resistance (thermal stability) of the film after firing. Thus, a reactive compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor can be contained.

  Examples of the thermosetting resin include epoxy resins, cyanate ester resins, unsaturated polyester resins, benzoxazine resins, benzoxazolines, phenol resins, melamine resins, maleimide compounds, and blocked isocyanates.

  Examples of the compound having reactivity with the polyimide precursor include a compound capable of reacting with a carboxyl group, amino group or terminal acid anhydride in a polymer to form a three-dimensional crosslinked structure. Among them, a thermal base generator compound that generates an amino group that is a base by heating is preferable. For example, it can be obtained by protecting an amino group of a base compound such as an amine with an acid chloride compound, which is protected with a dicarbonate compound represented by the general formula (7), which forms a salt structure with an acid such as sulfonic acid.

（式（７）中、Ｒ１９は炭素数１〜炭素数２０の２価の有機基を表し、Ｒ２０は、炭素数１〜炭素数２０の１価の有機基を表す。）

(In Formula (7), R19 represents a C1-C20 divalent organic group, and R20 represents a C1-C20 monovalent organic group.)

Thereby, it is stable and does not express basicity at room temperature, and it can be set as the thermal base generator which deprotects by heating and generates a base. The thermal base generator has the effect of increasing the molecular weight of the polymer skeleton by reacting with the terminal acid anhydride in the polymer (stretching the molecule). It is useful in that it exhibits performance such as solvent resistance. In addition, from the viewpoint of solvent resistance and flame retardancy, as the thermal base generator, a compound obtained by protecting the amino group of a basic compound such as an amine with the dicarbonate compound represented by the general formula (7) is used. R ₁₉ is preferably -Ar-Z-Ar-, -Ar-Z-Ar-Z-Ar-, or -Ar-Z-Ar-Z- from the viewpoint of production and solvent resistance. Ar—Z—Ar—, and Z is preferably O, SO ₂ , or C (CH ₃ ) ₂ . Further, R ₁₉ is —Ar—Z—Ar— or —Ar—Z—Ar—Z—Ar—, and Z is particularly preferably O or SO ₂ (wherein Ar represents an aromatic ring). ). These have affinity with the aromatic ring of the acid dianhydride represented by the above general formula (3) or the above general formula (4) in which the aromatic ring in the thermal base generator constitutes the polyimide precursor Is preferable in terms of improving compatibility. Furthermore, by having an aromatic ring in the thermal base generator, the diamine after deprotection has a state of having an aromatic ring, and this diamine is bonded between the polymers, thereby giving bending resistance after firing, It is also presumed that the solvent property appears. In particular, when the diamine is used, due to the interaction between the diamine having an aromatic ring and the acid dianhydride component of the general formula (3) or the general formula (4) having an aromatic ring. It is presumed that diamine facilitates bonding between polymers. In addition, R ₂₀ corresponding to the protecting group is preferably an alkyl group having 2 to 10 carbon atoms from the viewpoint of easy deprotection. This is presumed that deprotection at a temperature lower than the temperature at which the polyimide precursor is calcined becomes possible by having 2 to 10 carbon atoms.

  The addition amount of the compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor is 50 mass from the viewpoint of developability when the amount of the polyimide precursor is 100 mass parts. Part or less is preferable, and 40 parts by weight or less is more preferable.

(E) Phosphorus compound The photosensitive resin composition according to the present invention preferably contains a phosphorus compound. The phosphorus compound is not limited as long as it is a compound containing a phosphorus atom in the structure. Examples of such phosphorus compounds include phosphate ester compounds and phosphazene compounds.

  Phosphoric acid ester compounds such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate, tris (2-ethylhexyl) phosphate, phosphate ester compounds having tris (2-ethylhexyl) phosphate as substituents, tris (butoxyethyl) phosphate Aromatic organic groups such as phosphate ester compounds, triphenyl phosphates, tricresyl phosphates, trixylenyl phosphates, resorcinol bis (diphenyl phosphates) with aliphatic organic groups containing oxygen atoms as substituents And phosphoric acid ester compounds. Among these, tris (butoxyethyl) phosphate and triisobutyl phosphate are preferable from the viewpoint of developability.

Examples of the phosphazene compound include structures represented by the following general formula (11) and the following general formula (12).

R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ in the phosphazene compound represented by the general formula (11) and the general formula (12) are not limited as long as they are organic groups having 1 to 20 carbon atoms. A carbon number of 1 or more is preferable because flame retardancy tends to be exhibited. A carbon number of 20 or less is preferred because it tends to be compatible with the polyimide precursor. Among these, from the viewpoint of flame retardancy, a functional group derived from an aromatic compound having 6 to 18 carbon atoms is particularly preferable. As such a functional group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group, 4-hydroxyphenyl group, 2-cyanophenyl Group, functional group having a phenyl group such as 3-cyanophenyl group and 4-cyanophenyl group, functional group having a naphthyl group such as 1-naphthyl group and 2-naphthyl group, pyridine, imidazole, triazole, tetrazole and the like. And functional groups derived from nitrogen heterocyclic compounds. These compounds having functional groups may be used alone or in combination of two or more as required. Among these, a compound having a phenyl group, a 3-methylphenyl group, a 4-hydroxyphenyl group, and a 4-cyanophenyl group is preferable because of availability.

  V in the phosphazene compound represented by the general formula (11) is not limited as long as it is 3 or more and 25 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 25 or less, the solubility in an organic solvent is high. Among these, it is preferable that v is 3 or more and 10 or less because of availability.

  The w in the phosphazene compound represented by the general formula (12) is not limited as long as it is 3 or more and 10,000 or less. When it is 3 or more, flame retardancy is exhibited, and when it is 10,000 or less, the solubility in organic solvents is high. Among these, 3 or more and 100 or less are preferable in view of availability.

D and E in the phosphazene compound represented by the general formula (12) are not limited as long as they are organic groups having 3 to 30 carbon atoms. In this, as the _{D, -N = P (OC 6} H 5) 3, -N = P (OC 6 H 5) 2 (OC 6 H 4 OH), - N = P (OC 6 H 5) ( _{OC 6 H 4 OH) 2,} -N = P (OC 6 H 4 OH) 3, -N = P (O) (OC 6 H 5), - N = P (O) (OC 6 H 4 OH), _{-N = P (OC 6 H 5} ) 2 (OC 6 H 4 CN), - N = P (OC 6 H 5) (OC 6 H 4 CN) 2, -N = P (OC 6 H 4 CN) 3 _{, -N = P (O) (} OC 6 H 4 CN) , etc. are preferable.

The _{E, -P (OC 6 H 5} ) 4, -P (OC 6 H 5) 3 (OC 6 H 4 OH), - P (OC 6 H 5) 2 (OC 6 H 4 OH) 2, - _{P (OC 6 H 5) (} OC 6 H 4 OH) 3, -P (OC 6 H 4 OH) 4, -P (O) (OC 6 H 5) 2, -P (O) (OC 6 H 4 _{OH) 2, -P (O)} (OC 6 H 5) (OC 6 H 4 OH), - N = P (OC 6 H 5) 2 (OC 6 H 4 CN), - N = P (OC 6 H _{5) (OC 6 H 4 CN} ) 2, -N = P (OC 6 H 4 CN) 3, is preferably such as _{-N = P (O) (OC} 6 H 4 CN).

  As the phosphorus compound, one kind may be used, or two or more kinds may be used in combination.

  In the photosensitive resin composition, the addition amount of the phosphorus compound is preferably 50 parts by mass or less from the viewpoint of developability and the like when the amount of the polyimide precursor is 100 parts by mass. From the viewpoint of flame retardancy of the cured product, 45 parts by mass or less is preferable, and 40 parts by mass or less is more preferable.

  The photosensitive resin composition can contain other compounds as long as the performance is not adversely affected. Specific examples thereof include heterocyclic compounds for improving adhesion and pigments and dyes for coloring the film.

The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Here, examples of the hetero atom include oxygen, sulfur, nitrogen, and phosphorus. Specific examples of the heterocyclic compound include 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, substituted imidazole such as 2-phenylimidazole, and N-type such as 1,2-dimethylimidazole. Alkyl group-substituted imidazole, aromatic group-containing imidazole such as 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4- Imidazole compounds such as methylimidazole, 1-cyanoethyl-2-undecylimidazole, cyano group-containing imidazole such as 1-cyanoethyl-2-phenylimidazole, and silicon-containing imidazole such as imidazolesilane, 5-mercaptotriazol , 5-methylbenzotriazole, 1- (1 ', 2'-di-carboxyethyl benzotriazole), 1- (2-ethylhexyl Le aminomethyl benzotriazole) triazole compounds such as 2-methyl-5-phenyl benzoxazole, etc. And the oxazole compound.

  Examples of pigments and dyes include phthalocyanine compounds.

  The addition amount of another compound will not be limited if it is 0.01 mass part or more and 30 mass parts or less. If it is 0.01 mass part or more, there exists a tendency for adhesiveness and the coloring property to a film to fully improve, and if it is 30 mass parts or less, there will be no bad influence on photosensitivity. The photosensitive resin composition may optionally contain an organic solvent.

  The organic solvent is not limited as long as it can uniformly dissolve and / or disperse the polyimide precursor. Examples of such organic solvents include dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and other ether compounds having 2 to 9 carbon atoms; acetone, methyl ethyl ketone A ketone compound having 2 to 6 carbon atoms; a saturated hydrocarbon compound having 5 to 10 carbon atoms such as normal pentane, cyclopentane, normal hexane, cyclohexane, methylcyclohexane, and decalin; benzene, toluene, Aromatic hydrocarbon compounds having 6 to 10 carbon atoms such as xylene, mesitylene and tetralin; methyl acetate, ethyl acetate, γ-butyrolactone, benzo Ester compounds having 3 to 9 carbon atoms such as methyl acid; halogen-containing compounds having 1 to 10 carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; acetonitrile, N, N-dimethyl Examples thereof include nitrogen-containing compounds having 2 to 10 carbon atoms such as formamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; and sulfur-containing compounds such as dimethyl sulfoxide.

  These may be one kind or a mixture of two or more kinds as required. Particularly preferable organic solvents include ether compounds having 2 to 9 carbon atoms, ester compounds having 3 to 9 carbon atoms, aromatic hydrocarbon compounds having 6 to 10 carbon atoms, and 2 or more carbon atoms. Examples thereof include nitrogen-containing compounds having 10 or less carbon atoms.

  Moreover, 1 type or 2 or more types of mixtures may be sufficient as needed. From the viewpoint of solubility of the polyimide precursor, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, and N, N-dimethylacetamide are preferable.

  The density | concentration of the polyimide precursor in the resin composition which consists of a polyimide precursor and an organic solvent will not be restrict | limited especially if it is a density | concentration which can synthesize | combine a resin molding. The concentration of the polyimide precursor is preferably 1% by mass or more from the viewpoint of the film thickness of the resin molded body to be produced, and the concentration of the polyimide precursor is preferably 90% by mass or less from the uniformity of the film thickness of the resin molded body. From the viewpoint of the film thickness of the obtained resin molding, it is more preferably 2% by mass or more and 80% by mass or less.

(F) Photosensitive film The photosensitive resin composition which concerns on this invention can be used suitably as a photosensitive film. The photosensitive film which concerns on this invention is equipped with the support film as a base material, and the said photosensitive resin composition provided on the support film. In the photosensitive film according to the present invention, a carrier film may be provided on one side. Furthermore, in the photosensitive film which concerns on this invention, you may provide a cover film in addition to these structures.

  From the viewpoint of producing a photosensitive film, the concentration of the polyimide precursor in the photosensitive resin composition is preferably 1% by mass or more and 90% by mass or less. The concentration of the polyimide precursor is preferably 1% by mass or more from the viewpoint of the film thickness of the photosensitive film, and preferably 90% by mass or less from the viewpoint of the viscosity and film thickness uniformity of the photosensitive resin composition. From the viewpoint of the film thickness of the resulting photosensitive film, it is more preferably 2% by mass or more and 80% by mass or less.

Next, the manufacturing method of a photosensitive film is demonstrated.
First, the substrate is coated with the photosensitive resin composition. As a base material, if it is a base material which is not damaged in the case of photosensitive dry film formation, it will not be limited. Examples of such a substrate include a silicon wafer, glass, ceramic, heat resistant resin, and carrier film. Examples of the carrier film include a polyethylene terephthalate film and a metal film. A heat-resistant resin and a carrier film are preferable from the viewpoint of easy handling, and a polyethylene terephthalate film is particularly preferable from the viewpoint of peelability after pressure bonding to the substrate.

  Examples of the coating method include bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, spin coating, slit coating, and brush coating. After the coating, if necessary, a heat treatment called pre-baking may be performed with a hot plate or the like.

  When using a photosensitive film composed of a photosensitive resin composition, the solution of the photosensitive resin composition is coated on an arbitrary substrate by an arbitrary method and then dried to form a dry film, for example, a carrier film and a photosensitive film. It is set as the laminated film which has a film.

  Moreover, it is good also as a laminated | multilayer film by providing at least one layer of arbitrary antifouling and protective cover films on a photosensitive film. In the laminated film according to the present invention, the cover film is not limited as long as it is a film that protects a photosensitive film such as low-density polyethylene.

  Next, a flexible printed wiring board can be obtained by pressure-bonding the photosensitive film to a substrate having wiring so as to cover the wiring, performing alkali development, and firing.

  Examples of the substrate having wiring in the flexible printed wiring board include a hard substrate such as a glass epoxy substrate and a glass maleimide substrate, or a flexible substrate such as a copper-clad laminate. Among these, a flexible substrate is preferable from the viewpoint of bendability.

  In the formation method of the said flexible printed wiring board, if the said photosensitive film is formed in a base material so that wiring may be covered, it will not be limited. As such a forming method, a method of performing hot pressing, thermal laminating, thermal vacuum pressing, thermal vacuum laminating or the like in a state where the wiring side of the substrate having the wiring and the photosensitive film according to the present invention are in contact with each other. Etc. Among these, from the viewpoint of embedding the photosensitive film between the wirings, a thermal vacuum press and a thermal vacuum lamination are preferable.

  The heating temperature for laminating the photosensitive film on the substrate having the wiring is not limited as long as the photosensitive film can be adhered to the substrate. From the viewpoint of adhesion to the substrate and from the viewpoint of decomposition of the photosensitive film and side reactions, 30 ° C. or more and 400 ° C. or less are preferable. More preferably, it is 50 degreeC or more and 150 degrees C or less.

  The surface treatment of the substrate having the wiring is not particularly limited, and examples thereof include hydrochloric acid treatment, sulfuric acid treatment, and sodium persulfate aqueous solution treatment.

  When the photosensitive film is a positive type, positive type photolithography can be performed by dissolving the light irradiation site by alkali development after the light irradiation. In the case where the photosensitive film is a negative type, negative type photolithography can be performed by dissolving the portion other than the light irradiated portion by alkali development after the light irradiation. In this case, examples of the light source used for light irradiation include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a fluorescent lamp, a tungsten lamp, an argon laser, and a helium cadmium laser. Among these, a high pressure mercury lamp and an ultrahigh pressure mercury lamp are preferable.

  The alkaline aqueous solution used for development is not limited as long as it is a solution capable of dissolving the light irradiation site when the photosensitive film is positive, and other than the light irradiation site when the photosensitive film is negative. Examples of such a solution include a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a tetramethylammonium hydroxide aqueous solution. From the viewpoint of developability, an aqueous sodium carbonate solution and an aqueous sodium hydroxide solution are preferred. Examples of the development method include spray development, immersion development, and paddle development.

  Next, the printed wiring board is formed by firing the printed wiring board to which the photosensitive film is pressure-bonded. Firing is preferably carried out at a temperature of 30 ° C. or higher and 400 ° C. or lower from the viewpoints of solvent removal, side reactions and decomposition. More preferably, it is 100 degreeC or more and 300 degrees C or less.

  The reaction atmosphere in the firing can be performed in an air atmosphere or an inert gas atmosphere. In the method for producing a printed wiring board, the time required for the baking varies depending on the reaction conditions, but is usually within 24 hours, particularly preferably in the range of 1 to 8 hours.

  The polyimide precursor and photosensitive resin composition according to the present invention have good warpage after curing and good developability, and exhibit chemical resistance when used as a cured product. Protective layer formation of printed wiring boards and circuit boards used for operation panels of electronic devices, insulating layer formation of laminated substrates, silicon wafers used in semiconductor devices, semiconductor chips, peripheral members of semiconductor devices, semiconductor mounting substrates It is used for film formation on electronic parts for protection, insulation and adhesion of heat sinks, lead pins, semiconductors, etc. A protective film that protects wiring formed on a silicon wafer, a copper clad laminate, a printed wiring board, or the like is called a coverlay.

  The resin composition according to the present invention can be made into a coverlay or a flexible printed wiring board by imidization. Furthermore, it is good also as a laminated body by providing the coverlay which imidized the resin composition which concerns on this invention on a copper clad laminated board.

  In addition, the polyimide precursor and the photosensitive resin composition according to the present invention include a flexible printed circuit (FPC) substrate, a tape automation bonding (TAB) substrate, an electrical insulating film and a liquid crystal display substrate in various electronic devices, It can be suitably used for an organic electroluminescence (EL) display substrate, an electronic paper substrate, a solar cell substrate, particularly a coverlay for a flexible printed circuit.

  Next, description will be made based on examples carried out in order to clarify the effects of the present invention. In addition, this invention is not limited at all by the following examples.

<Reagent>
In the following Examples and Comparative Examples, TMEG (trade name: TMEG-100 (manufactured by Shin Nippon Chemical Co., Ltd.)), BTDA (manufactured by Daicel Chemical), BPDA (manufactured by Mitsui Chemicals), 5BTA (black) Kinkasei), TMAB (trade name: CUA-4, manufactured by Ihara Chemical Industry Co., Ltd.), BAPP (manufactured by Wakayama Seika Kogyo Co., Ltd.), APB (trade name: APB-N (manufactured by Mitsui Chemicals)), DAS ( Huntsman), Jeffermin (trade name: Jeffermin XTJ-542, manufactured by Huntsman), Jeffermin (trade name: Jeffermin ED-900, manufactured by Huntsman), Jeffermin (trade name: Jeffermin D-2000) , Manufactured by Huntsman), maleic anhydride (manufactured by Wako Pure Chemical Industries), nadic anhydride (manufactured by Hitachi Chemical Co., Ltd.), phosphazene compound (trade name: FP-3) 0, manufactured by Fushimi Pharmaceutical), phosphazene compound (trade name: FP-300, manufactured by Fushimi Pharmaceutical), blocked isocyanate (trade name: TPA-B80E, manufactured by Asahi Kasei Chemicals), blocked isocyanate (trade name: SBN-70D) Asahi Kasei Chemicals), one-end blocked isocyanate (trade name: Karenz MOI-BP, Showa Denko), EO-modified bisphenol A dimethacrylate (trade name: BPE-500, Shin-Nakamura Chemical Co., Ltd.), pentaerythritol Tri / tetra (meth) acrylate (trade name: Aronix M-306, manufactured by Toagosei Co., Ltd.), Ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (trade name: IRGACURE OXE 02, manufactured by Ciba Japan ), Toluene (manufactured by Wako Pure Chemical Industries, for organic synthesis), γ-butyrolactone (manufactured by Wako Pure Chemical Industries), triethylene glycol dimethyl ether (manufactured by Wako Pure Chemical Industries), sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) ), 1,2-naphthoquinonediazide-5-sulfonic acid ester (trade name: PA-6, manufactured by Daito Chemix) The above-mentioned compound b (see the above general formula (9) and the above general formula (10)) is special. Used in the reaction without any purification.

<Weight average molecular weight measurement>
The weight average molecular weight was measured under the following conditions using gel permeation chromatography (GPC). Using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) as a solvent, 24.8 mmol / L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity before measurement) 99.5%) and 63.2 mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high performance liquid chromatograph) were used.
Column: Shodex KD-806M (manufactured by Showa Denko KK)
Flow rate: 1.0 mL / min Column temperature: 40 ° C
Pump: PU-2080 Plus (manufactured by JASCO)
Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)
UV-2075 Plus (UV-VIS: UV-Visible Absorber, manufactured by JASCO)
A calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

<Film thickness measurement>
The film thickness of the cured product was measured using a film thickness meter (ID-C112B manufactured by Mitutoyo).

<Dry film manufacturing method>
The dry film was manufactured by coating a photosensitive resin composition on a PET film (N152Q, manufactured by Teijin DuPont Films) as a base material. The coating method of the photosensitive resin composition was performed by a doctor blade method using FILMCOATER (manufactured by TESTER SANGYO, PI1210). The photosensitive resin composition was dropped onto a PET film and coated with a clearance of 150 μm. The coated film was dried at 95 ° C. for 30 minutes using a dryer (SPHH-10L, manufactured by ESPEC) to obtain a photosensitive dry film.

<Tack evaluation>
The presence or absence of tackiness of the photosensitive layer after drying at 95 ° C. for 30 minutes was evaluated by palpation. Those with fingerprints were marked with ×, and those without fingerprints were marked with ○.

<Lamination conditions>
Lamination was performed using a vacuum press (manufactured by Meiki Seisakusho). The press temperature was 70 ° C., the press pressure was 0.5 MPa, and the press time was 30 seconds.

<Developability evaluation>
The developability was evaluated with an optical microscope under the following conditions. After laminating on a copper-clad laminate using a photosensitive dry film under the above laminating conditions, in the case of a positive photosensitive resin composition, using a positive mask, the irradiation dose is 1.0 J / cm ² . In the case of a negative photosensitive resin composition, exposure was performed at 30 to 270 mJ / cm ² . Next, alkali development with an aqueous sodium carbonate solution and rinsing with water were performed, and the pattern was evaluated with an optical microscope after drying. A circular pattern having a 100 μm diameter (interval of 100 μm pitch) was used as the mask. A case where the copper surface appeared in the exposed area due to development and the remaining film ratio was 75% or more was evaluated as ◯, and a case where the resolution was inferior or the film thickness was less than 75% was evaluated as x.

<Measurement of warpage after firing>
The obtained photosensitive dry film was laminated on Kapton (registered trademark) under the above-mentioned lamination conditions, and then baked at 120 ° C. for 1 hour and then at 180 ° C. for 1 hour. The film after baking was cut out into 5 cm square, the thing with the floating height of the edge part within 10 mm was set as (circle), and the thing with the floating height more than it was set as x.

<Bending test after firing>
The film obtained after firing (curing) was folded at 180 degrees (goose folding), and cracking and peeling of the cover film were visually observed. The case where there was no cracking or peeling was rated as ◯, and the case where there was cracking or peeling was marked as x.

<Solvent resistance evaluation>
The solvent resistance was evaluated by the remaining film rate under the following measurement conditions. The film obtained after curing was cut into 5 cm square, immersed in a 2.38 mass% TMAH solution at 50 ° C. for 2 minutes, and the remaining film ratio was measured from the film thickness before and after immersion.

<Flame retardance evaluation>
The flame retardancy was evaluated by a flame retardancy test under the following conditions. After laminating on a polyimide film (Kapton EN-100 trade name, manufactured by Toray DuPont Co., Ltd.) using a photosensitive dry film under the above laminating conditions, firing was performed at 120 ° C. for 1 hour and subsequently at 180 ° C. for 1 hour. It was.

  The obtained film was cut into a width of 1 cm and a length of 5 cm. Next, the process of igniting one end of the test piece and spreading it was visually observed. A sample that was extinguished during the course was marked with ◯, and a sample that had all burned was marked with ×.

<Thermal stability evaluation>
The thermal stability was evaluated by the rate of change of the weight average molecular weight of the polyimide precursor before and after coating . A polyimide precursor was produced by the dry film production method, and the obtained dry film was dissolved in the GPC measurement solvent, and then the weight average molecular weight was measured by GPC. About the obtained weight average molecular weight, it performed by calculating | requiring the rate of change from the weight average molecular weight by GPC which melt | dissolved the polyimide precursor solution before coating drying in the said GPC measurement solvent, and was measured.

<IR spectrum measurement>
The IR spectrum was measured under the following conditions. A polyimide resin precursor and / or a photosensitive resin composition is applied onto the copper foil using a hand coater so that the film thickness after drying is 17 μm, and the coated sample is placed in a dryer at 30 ° C. for 30 minutes. Heated for minutes and dried. About the obtained film, IR spectrum was measured by the ATR method and / or the transmission method using the infrared spectrophotometer (The JASCO Corporation make, FT / IR-460Puls).

<Glass transition temperature: Tg>
The glass transition temperature was measured using a thermomechanical analyzer (manufactured by Shimadzu Corporation, TMA-50). By thermomechanical analysis, the test piece elongation was measured at a load of 5 g, a heating rate of 10 ° C./min, under a nitrogen atmosphere (flow rate of 20 ml / min) and a temperature of 50 to 450 ° C. The glass transition temperature of the polyimide film after firing was determined.

(Synthesis example 1) The synthesis | combination of the thermal base generator 1 In a nitrogen atmosphere, the 2L isobaric dropping funnel was installed in the 18L enamel tank, and it deaerated. Thereafter, tetrahydrofuran (1683 g) and 3,4'-oxydianiline (3 mol) were added to an 18 L enamel tank, and di-t-butyl dicarbonate (6.2 mol) was added to tetrahydrofuran (1000 g) in a 2 L isobaric dropping funnel. The solution diluted with was added. This solution was added dropwise over 165 minutes so that the internal temperature in the 18 L enamel tank was 22 ° C. or lower. Then, it was made to react at 50 degreeC for 21 hours, stirring. Thereafter, ion-exchanged water (4.8 L) and ethyl acetate (3.6 L) were added to a 30 L extractor, and extraction and liquid separation were performed to obtain a reddish brown transparent organic layer. The solvent was distilled off from the organic layer with a 50 L evaporator. The residue was crystallized from hexane (3.6 L) and ethanol (360 ml), filtered, and then dried in vacuo to obtain a thermal base generator 1 represented by the following general formula (13) as a light brown solid. .

  The result of the IR spectrum of the thermal base generator 1 measured by the IR spectrum measuring method is shown in FIG. 1, and the peak appearance position is shown below.

Peak appearance position (cm ⁻¹ ): 3300, 2978, 1691, 1602, 1541, 1508, 1440, 1367, 1281, 1243, 1214, 1157, 1055, 984, 879, 838, 776

(Synthesis example 2) The synthesis | combination of the thermal base generator 2 The thermal base generator 2 was obtained according to the method described in the synthesis example 1 except having used APB as a diamine in the synthesis example 1.

(Synthesis Example 3) Synthesis of Thermal Base Generator 3 According to the method described in Synthesis Example 1 except that DAS was used as the diamine in Synthesis Example 1, a thermal base generator 3 was obtained.

[Example 1]
In a nitrogen atmosphere, Jeffermine XTJ-542 (18.6 mmol), γ-butyrolactone (60 g), 5BTA (60 mmol), and toluene (75 g) were placed in a separable flask equipped with a Dean-Stark apparatus and a refluxer at 50 ° C. And stirred for 1 hour. Subsequently, the mixture was heated and stirred at 180 ° C. for 2 hours. Further, toluene as an azeotropic solvent was removed over 2.5 hours, and then cooled to 25 ° C. Subsequently, APB-N (37.2 mmol) and γ-butyrolactone (45.6 g) were added and stirred at 70 ° C. for 5 hours to obtain a γ-butyrolactone solution of the polyimide precursor (1). The weight average molecular weight of the polyimide precursor (1) and the results of thermal stability evaluation are shown in Table 1 below.

The result of the IR spectrum of the polyimide precursor (1) measured by the IR spectrum measurement method is shown in FIG. 2, and the peak appearance position is shown below.
Peak appearance position (cm ⁻¹ ): 2941, 2866, 1780, 1719, 1594, 1542, 1480, 1438, 1376, 1288, 1249, 1179, 1111, 987, 864, 731

  Table 1 below shows the results of weight average molecular weight, C / (A + B + C), and thermal stability evaluation.

Next, with respect to 100 parts by mass of the polyimide precursor (1), BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) ) were mixed and the photosensitive resin composition (1) was made adjustment.

  For photosensitive resin composition (1), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 3%.

[Example 2]
In Example 1, a photosensitive resin composition (2) was prepared according to the method described in Example 1 except that FP-300 was used instead of FP-390 as the phosphazene compound.

  For photosensitive resin composition (2), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 4%.

[Example 3]
In a 500 mL separable flask equipped with a Dean-Stark apparatus and a reflux under a nitrogen atmosphere, Jeffamine XTJ-542 (6.2 mmol), γ-butyrolactone (30 g), 5BTA (20 mmol), and toluene (25 g) were placed. Pyridine (4.8 mmol) and γ-valerolactone (2.4 mmol) were added as a catalyst, and the mixture was heated and stirred at 140 ° C. for 6 hours under a nitrogen stream (400 mL / min) to remove toluene and the catalyst as an azeotropic solvent. . The reaction solution was cooled to 25 ° C., then APB-N (12.4 mmol) and γ-butyrolactone (5.2 g) were added, and the mixture was stirred at 70 ° C. for 5 hours to obtain γ-butyrolactone of polyimide precursor (2). A solution was obtained. The weight average molecular weight of the polyimide precursor (2) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (2). And a photosensitive resin composition (3) was prepared.

  For photosensitive resin composition (3), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 3%.

[Example 4]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 18.85 mmol) and 5BTA (60.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (37.2 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of polyimide precursor (3). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (3) and the results of thermal stability evaluation are shown in Table 1 below.

  The result of the IR spectrum of the polyimide precursor (3) measured by the IR spectrum measuring method is shown in FIG. 3, and the peak appearance position is shown below.

Peak appearance position (cm ⁻¹ ): 2936, 2868, 1773, 1717, 1595, 1543, 1480, 1438, 1373, 1247, 1180, 1154, 1105, 989, 861, 731

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (3). And a photosensitive resin composition (4) was prepared.

  For photosensitive resin composition (4), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 4%.

[Example 5]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 14.85 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., APB-N (21.41 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (4). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (4) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (4). And a photosensitive resin composition (5) was prepared.

  For photosensitive resin composition (5), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.

[Example 6]
In Example 5, the photosensitive resin composition (6) was prepared according to the method described in Example 5, except that FP-300 was used instead of FP-390 as the phosphazene compound.

  For photosensitive resin composition (6), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.

[Example 7]
In Example 5, a polyimide precursor (5) was used in accordance with the method described in Example 5 except that (trade name: Jeffamine ED-900 (manufactured by Huntsman)) was used instead of Jeffamine XTJ-542 as the diamine. ) Was polymerized. The weight average molecular weight, C / (A + B + C) of the polyimide precursor (5) and the results of thermal stability evaluation are shown in Table 1 below.

  In the same manner as in Example 5, a photosensitive resin composition (7) was prepared. About 1% by weight sodium carbonate of the photosensitive resin composition (7), evaluation of alkali developability in a 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, warping of the film after firing Measurement and glass transition temperature measurement were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.

[Example 8]
In Example 5, the polyimide precursor (6 ) Was polymerized. The weight average molecular weight, C / (A + B + C) of the polyimide precursor (6) and the results of thermal stability evaluation are shown in Table 1 below.

  In the same manner as in Example 5, a photosensitive resin composition (8) was prepared. For photosensitive resin composition (8), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.

[Example 9]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 10 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (21.41 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (7). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (7) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (7). And a photosensitive resin composition (9) was prepared.

  For photosensitive resin composition (9), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.

[Example 10]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 14.3 mmol) and BTDA (52.14 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (33.18 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (8). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (8) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass), TPA with respect to 100 parts by mass of the polyimide precursor (8). -B80E (5 mass parts) was mixed and the photosensitive resin composition (10) was adjusted.

  About the photosensitive resin composition (10), evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 15%.

[Example 11]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol) and BPDA (47.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (9). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (9) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (9). And a photosensitive resin composition (11) was prepared.

  About the photosensitive resin composition (11), evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 30%.

  The result of the IR spectrum of the photosensitive resin composition after firing measured by the above IR spectrum measurement method is shown in FIG. 4, and the peak appearance position is shown below.

Peak appearance position (cm ⁻¹ ): 2866, 1773, 1717, 1589, 1488, 1372, 1239, 1179, 1105, 948, 884, 845, 741

[Example 12]
In Example 11, a photosensitive resin composition (12) was prepared according to the method described in Example 11 except that FP-300 was used instead of FP-390 as the phosphazene compound.

  For photosensitive resin composition (12), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 25%.

[Example 13]
In Example 11, a photosensitive resin composition (13) was prepared according to the method described in Example 11, except that TPA-B80E (5 parts by mass) was further mixed.

  For photosensitive resin composition (13), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 50%.

[Example 14]
In Example 12, a photosensitive resin composition (14) was prepared according to the method described in Example 11, except that TPA-B80E (5 parts by mass) was further mixed.

  For photosensitive resin composition (14), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 55%.

[Example 15]
In Example 12, a photosensitive resin composition (15) was prepared according to the method described in Example 11, except that SBN-70DT (5 parts by mass) was further mixed.

  For photosensitive resin composition (15), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 60%.

[Example 16]
In Example 12, a photosensitive resin composition (16) was prepared according to the method described in Example 11, except that Karenz MOI-BP (5 parts by mass) was further used.

  For photosensitive resin composition (16), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 58%.

[Example 17]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.9 mmol) and BPDA (47.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., DAS (25.08 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (10). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (10) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (10). And a photosensitive resin composition (17) was prepared.

  For photosensitive resin composition (17), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 65%.

[Example 18]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol), BPDA (31.72 mmol), and ODPA (15.86 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (11). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (11) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (11). And a photosensitive resin composition (18) was prepared.

  About the photosensitive resin composition (18), evaluation of alkali developability in a 1% by mass sodium carbonate aqueous solution, tackiness, bending test after firing, flame retardancy test, warpage measurement of the film after firing, glass transition temperature measurement Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 63%.

[Example 19]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.9 mmol), BPDA (31.72 mmol), and ODPA (15.86 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., then DAS (25.08 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (12). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (12) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (12). And a photosensitive resin composition (19) was prepared.

  For the photosensitive resin composition (19), evaluation of alkali developability in a 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 70%.

[Example 20]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol), BPDA (44.0 mmol), and maleic anhydride (3.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (13). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (13) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (13). And a photosensitive resin composition (20) was prepared.

  About the photosensitive resin composition (20), evaluation of alkali developability in a 1% by mass sodium carbonate aqueous solution, tackiness, bending test after firing, flame retardancy test, film warpage measurement after firing, glass transition temperature measurement Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 27%.

[Example 21]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 12.4 mmol), BPDA (44.0 mmol) and nadic anhydride (3.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., subsequently APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (14). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (14) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (14). And a photosensitive resin composition (21) was prepared.

  About the photosensitive resin composition (21), evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 28%.

[Example 22]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.9 mmol), BPDA (44.0 mmol) and maleic anhydride (3.58 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., DAS (25.08 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (15). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (15) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (15). And a photosensitive resin composition (22) was prepared.

  About photosensitive resin composition (22), evaluation of alkali developability in 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 26%.

[Example 23]
In a nitrogen atmosphere, a separable flask equipped with a Dean-Stark apparatus and a refluxer was charged with γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 16.0 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene which is an azeotropic solvent, the solution was cooled to 25 ° C., then BAPP (19.49 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (16). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (16) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (16). And a photosensitive resin composition (23) was prepared.

  For the photosensitive resin composition (23), evaluation of alkali developability in a 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of the film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 4%.

[Example 24]
In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 ( 10.4 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the solution was cooled to 25 ° C., followed by addition of TMAB (25.13 mmol), and stirred at 25 ° C. for 8 hours to obtain a solution of a polyimide precursor (17). The weight average molecular weight, C / (A + B + C) of the polyimide precursor (17) and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), and FP-300 (40 parts by mass) are mixed with 100 parts by mass of the polyimide precursor (17). Then, a photosensitive resin composition (24) was prepared.

  For photosensitive resin composition (24), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 3%.

[Example 25]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor (1) obtained in Example 1. A photosensitive resin composition (25) was prepared.

  For photosensitive resin composition (25), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 3%.

[Example 26]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor (3) obtained in Example 4. A photosensitive resin composition (26) was prepared.

  For photosensitive resin composition (26), evaluation of alkali developability in 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 4%.

[Example 27]
1,2-naphthoquinonediazide-5-sulfonic acid ester (PA6) (20 parts by mass) is mixed with 100 parts by mass of the polyimide precursor (1) obtained in Example 1, and a photosensitive resin composition ( 27) was adjusted.

  For photosensitive resin composition (27), evaluation of alkali developability in 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 68%.

[Example 28]
With respect to 100 parts by mass of the polyimide precursor (3) obtained in Example 4, BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (28).

  About the photosensitive resin composition (28), the alkali developability in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 95%.

[Example 29]
In Example 28, a photosensitive resin composition (29) was prepared according to the method described in Example 28, except that the thermal base generator 2 was used instead of the thermal base generator 1.

  For photosensitive resin composition (29), evaluation of alkali developability with 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 90%.

[Example 30]
In Example 28, a photosensitive resin composition (30) was prepared according to the method described in Example 28 except that the thermal base generator 3 was used instead of the thermal base generator 1.

  For photosensitive resin composition (30), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 94%.

[Example 31]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (9) obtained in Example 12. (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (31).

  About the photosensitive resin composition (31), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 98%.

[Example 32]
In Example 31, a photosensitive resin composition (32) was prepared according to the method described in Example 31 except that the thermal base generator 2 was used instead of the thermal base generator 1.

  For photosensitive resin composition (32), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 94%.

[Example 33]
In Example 31, a photosensitive resin composition (33) was prepared according to the method described in Example 31 except that the thermal base generator 3 was used instead of the thermal base generator 1.

  About photosensitive resin composition (33), evaluation of alkali developability in 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 95%.

[Example 34]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (13) obtained in Example 20. (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (34).

  About the photosensitive resin composition (34), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 81%.

[Example 35]
In Example 34, a photosensitive resin composition (35) was prepared according to the method described in Example 34 except that the thermal base generator 2 was used instead of the thermal base generator 1.

  For the photosensitive resin composition (35), evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 80%.

[Example 36]
In Example 34, a photosensitive resin composition (36) was prepared according to the method described in Example 34 except that the thermal base generator 3 was used instead of the thermal base generator 1.

  For photosensitive resin composition (36), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 80%.

[Example 37]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (14) obtained in Example 21. (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (37).

  About the photosensitive resin composition (37), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 84%.

[Example 38]
In Example 37, a photosensitive resin composition (38) was prepared according to the method described in Example 37, except that the thermal base generator 2 was used instead of the thermal base generator 1.

  For photosensitive resin composition (38), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 82%.

[Example 39]
In Example 37, a photosensitive resin composition (39) was prepared according to the method described in Example 37, except that the thermal base generator 3 was used instead of the thermal base generator 1.

  For photosensitive resin composition (39), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 83%.

[Example 40]
With respect to 100 parts by mass of the polyimide precursor (10) obtained in Example 17, BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (40).

  About the photosensitive resin composition (40), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 82%.

[Example 41]
In Example 40, the photosensitive resin composition (41) was prepared according to the method described in Example 40 except that the thermal base generator 2 was used instead of the thermal base generator 1.

  About photosensitive resin composition (41), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 81%.

[Example 42]
In Example 40, the photosensitive resin composition (42) was prepared according to the method described in Example 40 except that the thermal base generator 3 was used instead of the thermal base generator 1.

  For photosensitive resin composition (42), evaluation of alkali developability in 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 80%.

[Example 43]
BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-300 with respect to 100 parts by mass of the polyimide precursor (15) obtained in Example 22. (40 parts by mass) and thermal base generator 1 (5 parts by mass) were mixed to prepare a photosensitive resin composition (43).

  About the photosensitive resin composition (43), the alkali developability evaluation in 1 mass% sodium carbonate aqueous solution, tack property, the bending test after baking, a flame retardance test, and the curvature measurement of the film after baking were performed. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 86%.

[Example 44]
In Example 43, a photosensitive resin composition (44) was prepared according to the method described in Example 43, except that the thermal base generator 2 was used instead of the thermal base generator 1.

  For the photosensitive resin composition (44), evaluation of alkali developability in a 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 85%.

[Example 45]
In Example 44, a photosensitive resin composition (45) was prepared according to the method described in Example 44, except that the thermal base generator 3 was used instead of the thermal base generator 1.

  For photosensitive resin composition (45), evaluation of alkali developability in 1% by weight aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of warpage of film after firing, measurement of glass transition temperature Went. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 84%.

[Comparative Example 1]
Under a nitrogen atmosphere, a separable flask was charged with Jeffamine XTJ-542 (4.45 mmol), γ - butyrolactone (32.5 g), APB-N (9.05 mmol), 5 - BTA (15 mmol), and an oil bath. The temperature was gradually raised, and the mixture was heated and stirred at 60 ° C. for 3 hours. Further heating for 1 hour and stirred at 70 ° C., the polyimide precursor gamma - give the butyrolactone solution. The weight average molecular weight, C / (A + B + C) of the polyimide precursor of Comparative Example 1 and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 1, and the photosensitivity of Comparative Example 1 is obtained. A resin composition was prepared.

  About the photosensitive resin composition of Comparative Example 1, evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, glass transition temperature Measurements were made. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 32%.

[Comparative Example 2]
Under a nitrogen atmosphere, in a separable flask, γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 (14.85 mmol), APB-N ( 21.41 mmol) was added, followed by TMEG (39.0 mmol), and the mixture was stirred at 25 ° C. for 8 hours to obtain a polyimide precursor solution. The weight average molecular weight, C / (A + B + C) of the polyimide precursor of Comparative Example 2 and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 2, and the photosensitivity of Comparative Example 2 is obtained. A resin composition was prepared.

  About the photosensitive resin composition of Comparative Example 2, evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, glass transition temperature Measurements were made. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 52%.

[Comparative Example 3]
Under a nitrogen atmosphere, a separable flask was charged with γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 (14.85 mmol), APB-N ( 21.41 mmol) was added, followed by BTDA (39.0 mmol) and stirring at 25 ° C. for 8 hours to obtain a polyimide precursor solution of Comparative Example 3. The weight average molecular weight, C / (A + B + C) of the polyimide precursor of Comparative Example 3 and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 3, and the photosensitivity of Comparative Example 3 is obtained. A resin composition was prepared.

About the photosensitive resin composition of Comparative Example 3, evaluation of alkali developability in a 1 % by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, glass transition temperature Measurements were made. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the remaining film rate was 15%.

[Comparative Example 4]
Under a nitrogen atmosphere, in a separable flask, γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), Jeffamine XTJ-542 (14.85 mmol), APB-N ( 21.41 mmol) was added, followed by BPDA (39.0 mmol), and the mixture was stirred at 25 ° C. for 8 hours to obtain a polyimide precursor solution of Comparative Example 4. Table 1 below shows the weight average molecular weight, C / (A + B + C) and thermal stability evaluation results of the polyimide precursor of Comparative Example 4.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 4, and the photosensitivity of Comparative Example 4 is obtained. A resin composition was prepared.

About the photosensitive resin composition of Comparative Example 4, evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, glass transition temperature Measurements were made. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 61%.
[Comparative Example 5]

  In a nitrogen atmosphere, a separable flask equipped with a Dean Stark apparatus and a refluxer was charged with γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g), and APB-N (21. 41 mmol) and TMEG (39.0 mmol) were added, the temperature was raised to 180 ° C., and the mixture was heated and stirred at 180 ° C. for 1 hour. After removing toluene as an azeotropic solvent, the mixture was cooled to 25 ° C., then Jeffamine XTJ-542 (14.85 mmol) was added, and the mixture was stirred at 25 ° C. for 8 hours. Obtained. The weight average molecular weight, C / (A + B + C) of the polyimide precursor of Comparative Example 5 and the results of thermal stability evaluation are shown in Table 1 below.

  BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) are mixed with 100 parts by mass of the polyimide precursor of Comparative Example 5, and the photosensitivity of Comparative Example 5 is obtained. A resin composition was prepared.

  About the photosensitive resin composition of Comparative Example 5, evaluation of alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame retardancy test, measurement of film warpage after firing, glass transition temperature Measurements were made. The results are shown in Table 2 below. Moreover, when the solvent resistance to the TMAH solution of the film obtained after baking was evaluated, the residual film rate was 2%.

  As can be seen from the results in Tables 1 and 2, the polyimide precursors (Example 1 to Example 45) have a lower weight average molecular weight when dried at 95 ° C. than Comparative Examples 1 to 5. It can be seen that the thermal stability, the bending test, flame retardancy, warpage, developability, tackiness, and solvent resistance are good.

  In particular, as can be seen from Example 28 to Example 45, in the case where the thermal base generator 1 to the thermal base generator 3 having a specific structure is used, the remaining film ratio is greatly increased. It can be seen that the solvent property is good. As described above, this is considered to be due to an interaction between a diamine having an aromatic ring generated by thermal decomposition and a polyimide precursor having an aromatic ring. Further, as can be seen from Comparative Example 5, it can be seen that when the diamine having the specific structure is not contained in the polyimide structure, the thermal stability, the bending test, the flame retardancy, the developability, and the tackiness are lowered.

  The polyimide precursor is a semiconductor device surface protective film, an interlayer insulating film, a rewiring insulating film, a bump protective film, a multilayer circuit interlayer insulating film, a flexible copper clad cover coat, and a liquid crystal alignment It can be suitably used as a film or the like.

  This application is based on Japanese Patent Application No. 2009-261102 filed on Nov. 16, 2009. All this content is included here.

Claims (16)

(A) a polyimide precursor, and (B) a photosensitizer,
Wherein the (B) a photosensitive agent, having two or more photopolymerizable unsaturated double bond include (meth) acrylate compounds, see contains a further (C) a photopolymerization initiator,
The (A) polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively. The tetracarboxylic dianhydride constituting the polyimide precursor includes one or more tetracarboxylic dianhydrides selected from the group consisting of the following general formula (3) and the following general formula (4), and the polyimide The diamine constituting the structure includes a diamine represented by the following general formula (5), the polyamic acid structure represented by the following general formula (2) includes a diamine represented by the following general formula (8),
The diamine represented by the following general formula (8) is 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7 -Diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminobenz Anilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) Fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) Biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, trimethylene-bis (4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4 '- diamino biphenyl, is any one of 1,3-bis (4-aminophenoxy benzene) this The photosensitive resin composition characterized.

(In Formula (1) and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In formula (1) and formula (2), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and in the formula (2) and the formula (8), R ₁₇ has 1 carbon atom. -Represents a divalent organic group having 90 carbon atoms, wherein in formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in formula (4), Y represents an aromatic ring 2 Is .a representing the organic group or a divalent organic group with carbon number from 1 to 20 carbon atoms represents an integer of 1 to 20.) The (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds includes both a compound having two double bonds and a compound having three or more double bonds, The photosensitive resin composition according to claim 1 . (A) a polyimide precursor, and (B) a photosensitizer,
(B) the photosensitive agent, see containing a quinonediazide compound,
The (A) polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively. The tetracarboxylic dianhydride constituting the polyimide precursor includes one or more tetracarboxylic dianhydrides selected from the group consisting of the following general formula (3) and the following general formula (4), and the polyimide The diamine constituting the structure includes a diamine represented by the following general formula (5), the polyamic acid structure represented by the following general formula (2) includes a diamine represented by the following general formula (8),
The diamine represented by the following general formula (8) is 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7 -Diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminobenz Anilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) Fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) Biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, trimethylene-bis (4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4 '- diamino biphenyl, is any one of 1,3-bis (4-aminophenoxy benzene) this The photosensitive resin composition characterized.

(In Formula (1) and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In formula (1) and formula (2), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and in the formula (2) and the formula (8), R ₁₇ has 1 carbon atom. -Represents a divalent organic group having 90 carbon atoms, wherein in formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in formula (4), Y represents an aromatic ring 2 Is .a representing the organic group or a divalent organic group with carbon number from 1 to 20 carbon atoms represents an integer of 1 to 20.) (A) a polyimide precursor, and (B) a photosensitizer,
(D) including a reactive compound having reactivity with the polyimide precursor, the reactive compound is represented by the following formula (7) ,
The (A) polyimide precursor is a polyimide precursor having a polyimide structure represented by the following general formula (1) and a polyamic acid structure represented by the following general formula (2) as repeating structural units, respectively. The tetracarboxylic dianhydride constituting the polyimide precursor includes one or more tetracarboxylic dianhydrides selected from the group consisting of the following general formula (3) and the following general formula (4), and the polyimide The diamine constituting the structure includes a diamine represented by the following general formula (5), the polyamic acid structure represented by the following general formula (2) includes a diamine represented by the following general formula (8),
The diamine represented by the following general formula (8) is 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy). ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, 4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7 -Diamino-dimethyldibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, 4,4'-diaminobenz Anilide, 1,3-bis (4-aminophenoxy) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) Fluorene, 5-amino-1- (4-aminomethyl) -1,3,3-trimethylindane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) Biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane, trimethylene-bis (4-aminobenzoate), 4-aminophenyl-4-aminobenzoate, 2-methyl-4-aminophenyl-4-aminobenzoate, Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3′-dihydroxy-4,4 '- diamino biphenyl, is any one of 1,3-bis (4-aminophenoxy benzene) this The photosensitive resin composition according to any one of claims 1 to 3, characterized in.

(In Formula (1) and Formula (5), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon. Represents a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different, and in formula (1) and formula (5), R ₃ , R ₆ , R ₉ , R ₁₂ , R ₁₅ represents a tetravalent organic group having 1 to 20 carbon atoms, and m, n, and p each independently represent an integer of 0 to 100. In formula (1) and formula (2), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and in the formula (2) and the formula (8), R ₁₇ has 1 carbon atom. -Represents a divalent organic group having 90 carbon atoms, wherein in formula (3), X represents a single bond, a carbonyl group or a sulfonyl group, and in formula (4), Y represents an aromatic ring 2 Is .a representing the organic group or a divalent organic group with carbon number from 1 to 20 carbon atoms represents an integer of 1 to 20.)

(In the formula _{(7), R 19} is -Ar-Z-Ar- or -Ar-Z-Ar-Z- Ar- in and, Z is O or SO _2. The _{R 20} is 2 carbon atoms To an alkyl group having 10 carbon atoms. (D) according to any one of claims 1 to 3, characterized in that it comprises a reactive compound having one or more resins selected from the group consisting of a thermosetting resin and a polyimide precursor reactive Photosensitive resin composition. (E) The photosensitive resin composition according to any one of claims 1 to 5, characterized in that it comprises a phosphorus compound. The photosensitive resin composition according to claim 6 , wherein the (E) phosphorus compound has one or more structures selected from the group consisting of a phosphate ester structure and a phosphazene structure. The diamine represented by the said General formula (5) is a diamine represented by the following general formula (5-1), The photosensitive resin composition in any one of Claims 1-7 characterized by the above-mentioned. Thing .

(In Formula (5-1), R ₁₈ is C ₂ H ₄ or C ₄ H ₈ , m, n, and p are each independently an integer of 0 or more and 40 or less, and 12 ≦ (m + n + p) ≦ 40 is satisfied.) The said (A) polyimide precursor is represented by following General formula (6), The photosensitive resin composition in any one of Claims 1-8 characterized by the above-mentioned.

(In the formula (6), R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ , R ₁₄ are each independently a hydrogen atom or carbon number 1 to carbon. Represents a monovalent organic group having the number 20, and may be the same or different, and R ₃ , R ₆ , R ₉ , R ₁₂ , and R ₁₅ are each a tetravalent organic having 1 to 20 carbon atoms. And m, n and p each independently represents an integer of 0 to 100. R ₁₆ represents a tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4). R ₁₇ represents a divalent organic group having 1 to 90 carbon atoms, X represents a single bond, a carbonyl group, or a sulfonyl group, and Y represents an aromatic ring. Represents a divalent organic group containing 1 or an aliphatic divalent organic group having 1 to 20 carbon atoms, and a represents an integer of 1 to 20. .A, B, C represents the mol% of each unit, satisfy 0 <A <100,0 <B <100,0 <C <100,0.05 ≦ C / (A + B + C) ≦ 0.95.) (A) the polyimide precursor, a photosensitive resin composition according to any one of claims 1 to 9, characterized by being represented by the following general formula (6-1).

(In the formula (6-1), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the general formula (3) or the general formula (4), and R ₁₇ is Represents a divalent organic group having 1 to 90 carbon atoms, R ₁₈ is C ₂ H ₄ or C ₄ H ₈ , and m, n, and p are each independently an integer of 0 to 40. Yes 12 ≦ (m + n + p) ≦ 40) Photosensitive film to a support film layer, characterized in that it comprises a photosensitive resin composition according to claim 1 provided on the support film to claim 10. The photosensitive film according to claim 11 , comprising a carrier film on one surface. The photosensitive film according to claim 11 or claim 12, characterized by further comprising a cover film. A coverlay obtained by imidizing the photosensitive resin composition according to any one of claims 1 to 10 . The flexible printed wiring board characterized by being the structure which imidized the photosensitive resin composition in any one of Claims 1-10 . A laminate comprising the coverlay according to claim 14 and a copper clad laminate.

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