KR101392539B1 - Polyimide precursor and photosensitive resin composition containing the polyimide precursor - Google Patents

Abstract

(화학식 (1)∼화학식 (5)에서, R₁∼R₁₇은 수소 원자 또는 소정의 유기기를 나타내고, X는 소정의 치환기를 나타내고, Y는 소정의 유기기를 나타내고, a, m, n, p는 소정의 정수를 나타낸다.)The present invention relates to a polyimide precursor suitable for use as a cover layer of an FPC after firing with less bending of the FPC after firing in the case of being used for a flexible printed substrate (FPC) without cracking of the photosensitive layer, A photosensitive resin composition comprising the polyimide precursor, a photosensitive film using the photosensitive resin composition, a substrate obtained using the photosensitive film, and a laminated body thereof. The polyimide precursor of the present invention is a polyimide precursor having a polyimide structure represented by the following formula (1) and containing a diamine of the following formula (5), and a polyimide structure represented by the following formula (2) Of tetracarboxylic dianhydride as a repeating structural unit.

(1) to (5), R ₁ to R ₁₇ represent a hydrogen atom or a predetermined organic group, X represents a predetermined substituent, Y represents a predetermined organic group, and a, m, n, p Represents a predetermined integer.)

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition comprising a polyimide precursor and a polyimide precursor,

The present invention relates to a polyimide precursor having a polyamic acid structure and a polyimide structure as repeating structural units respectively and having an alkyl ether structure and selectively introducing an aliphatic diamine into the polyimide structure, a photosensitive resin composition comprising the polyimide precursor , A photosensitive film using the photosensitive resin composition, and a flexible printed substrate obtained using the photosensitive film and a laminated body thereof.

Recently, a film-type printed board called a flexible printed board (hereinafter also referred to as " FPC " The flexible printed circuit board has a structure including a coverlay formed of a polyimide film or the like on a wire-processed FCCL (Flexible Cupper Clad Laminate), and is mainly used in electronic devices such as mobile phones, notebook computers, and digital cameras have. Since the FPC maintains its function even when bent, it is an indispensable material for reducing the size and weight of electronic equipment. Particularly, in recent years, electronic devices typified by notebook computers are becoming smaller and lighter, and by adopting FPC in these products, they contribute to reduction of dimensions and weight of electronic devices, reduction of product cost, and simplification of design.

In order to make the FPC finer and thinner, the development of a photosensitive coverlay is energetically performed in order to perform fine processing by lithography. Among them, photosensitive coverlay using a polyimide precursor is expected as a coverlay excellent in resistance to bending resistance, heat resistance and electric insulation derived from polyimide.

In the conventional screen printing, there are problems such as a two-step process and a low screen printing resolution when a solvent removing process or double-side processing is performed. For this reason, it is desired to convert the photosensitive resin composition 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 comprising 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 poly A photosensitive resin composition containing a polyimide precursor having an amide acid structure (Patent Document 2) has been proposed. However, in the photosensitive resin composition described in Patent Document 1, the aliphatic diamine constituting the polyimide precursor exists in the polyamic acid structure, and in the photosensitive resin composition described in Patent Document 2, the polyimide precursor has a polyamic acid structure to be. Therefore, the lowering of the molecular weight of the varnish obtained by dissolving the photosensitive resin composition in a solvent becomes large. In addition, the lowering of the molecular weight in the baking (heating and drying) step in the production of a dry film likewise increases, the toughness of the film is lowered, and the problem that the photosensitive layer is scratched when the photosensitive dry film obtained is bent have. Furthermore, when the pattern is formed by lithography due to a decrease in the molecular weight of the polyimide precursor, the development time is not stable, the residual film ratio is lowered, the pattern shape is distorted, or the like There was a tendency to decrease the sex.

In addition, in the process of converting polyimide precursor to polyimide, warpage may occur in the FPC due to the stress caused by the cyclization reaction due to imidization of the desolvation or polyimide precursor. When the FPC is warped, there arises a problem such as poor adhesion between the FCCL and the coverlay, and high driving power of the electronic device including the FPC. Therefore, it is required to improve the warpage of the FPC having the coverlay on the copper wiring.

Patent Document 1: JP-A-2006-321924 Patent Document 2: JP-A-05-158237

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and it is an object of the present invention to provide a flexible printed circuit board (FPC) which has no cracks in the photosensitive layer, A photosensitive resin composition comprising the polyimide precursor, a photosensitive film using the photosensitive resin composition, and a flexible printed substrate obtained by using the photosensitive film and a laminated body thereof .

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

The polyimide precursor of the present invention is a polyimide precursor having a polyimide structure represented by the following formula (1) and a polyamic acid structure represented by the following formula (2) as repeating units, Wherein the tetracarboxylic dianhydride comprises at least one tetracarboxylic acid dianhydride selected from the group consisting of the following formula (3) and the following formula (4), wherein the diamine constituting the polyimide structure is represented by the following formula (5). ≪ / RTI >

(Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or a carbon number of 1 R ₃ , R ₆ , R ₉ , R ₁₂ and R _{15 each} represent a monovalent organic group having 1 to 20 carbon atoms and may be the same or different. In the formulas (1) and (5) And m, n and p each independently represent an integer of 0 to 100. In the formulas (1) and (2), R ₁₆ represents a tetracarboxylic acid represented by the formula (3) (4) wherein X represents a single bond, a carbonyl group, or a sulfonyl group, and R < ₁₇ > represents a divalent organic group having from 1 to 90 carbon atoms, , Y represents a divalent organic group having an aromatic ring or a divalent organic group having 1 to 20 carbon atoms, and a is an integer of 1 or more and 20 or less It represents.)

In the polyimide precursor of the present invention, it is preferable that the diamine represented by the formula (5) is a diamine represented by the following formula (5-1).

(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).

The polyimide precursor of the present invention is preferably represented by the following chemical formula (6).

(Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms 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, R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the above formula (3) or (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, Y represents a divalent organic group containing an aromatic ring or an aliphatic divalent organic group having 1 to 20 carbon atoms, and a is an integer of 1 or more and 20 or less 100, 0 <B <100, 0 <C <100, and 0 <A < 5? C / (A + B + C)? 0.95.

The polyimide precursor of the present invention is preferably represented by the following formula (6-1).

(6-1), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and R ₁₇ represents a tetravalent organic group having 1 to 90 carbon atoms represents a divalent organic group, R ₁₈ is C ₂ H ₄ or C ₄ H _8, and, m, n, p are each independently an integer of not less than 0 40 12≤ (m + n + p) ≤40.)

The photosensitive resin composition of the present invention is characterized by containing (A) the polyimide precursor and (B) a photosensitizer.

In the photosensitive resin composition of the present invention, it is preferable that (B) the photosensitive agent contains a (meth) acrylate compound having at least two photopolymerizable unsaturated double bonds, and (C) a photopolymerization initiator.

In the photosensitive resin composition of the present invention, it is preferable that the (meth) acrylate compound having at least two photopolymerizable unsaturated double bonds together includes a compound having two double bonds and a compound having three or more double bonds desirable.

In the photosensitive resin composition of the present invention, it is preferable that the photosensitive agent (B) contains a quinone diazide compound.

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

In the photosensitive resin composition of the present invention, it is preferable that (D) the reactive compound having reactivity with the polyimide precursor is represented by the following chemical formula (7).

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

In the photosensitive resin composition of the present invention, it is preferable to include the phosphorus compound (E).

In the photosensitive resin composition of the present invention, it is preferable that the phosphorus compound (E) has at least one structure selected from the group consisting of a phosphate ester structure and a phosphazene structure.

The photosensitive film of the present invention is characterized by including a support film layer and the photosensitive resin composition formed on the support film.

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

In the photosensitive film of the present invention, it is preferable to provide a cover film.

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

The flexible printed wiring board of the present invention is characterized by having a structure in which the above photosensitive resin composition is imidized.

The laminate of the present invention is characterized by comprising the coverlay and the copper-clad laminate.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyimide film which is suitable as a coverlay for an FPC with less bending of the FPC after firing in the case of being used for a flexible printed substrate (FPC) A photosensitive resin composition comprising the polyimide precursor, a photosensitive film using the photosensitive resin composition, and a flexible printed substrate obtained using the photosensitive film and a laminated body thereof.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an infrared absorption spectrum of a thermobase generator according to Synthesis Example 1 of the present invention. FIG.
2 is a diagram showing an infrared absorption spectrum of a polyimide precursor film according to Example 1 of the present invention.
3 is a diagram showing an infrared absorption spectrum of a polyimide precursor film according to Example 4 of the present invention.
4 is a diagram showing an infrared absorption spectrum of the photosensitive resin composition according to Example 11 of the present invention.

The present invention will be described in detail below.

(A) a polyimide precursor

The polyimide precursor is a polyimide precursor having a polyimide structure represented by the following formula (1) and a polyamic acid structure represented by the following formula (2) as repeating units, Wherein the tetracarboxylic acid dianhydride comprises at least one tetracarboxylic dianhydride selected from the group consisting of the following chemical formulas (3) and (4), and the diamine constituting the polyimide structure is represented by Chemical Formula (5) Is a diamine represented by the following formula (1).

R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom, R ₃ , R ₆ , R ₉ , R ₁₂ and R _{15 each} independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and may be the same or different. In the formulas (1) and (5) And m, n and p each independently represent an integer of 0 to 100. In the formulas (1) and (2), R ₁₆ represents a tetravalent organic group of the formula (3) And R ₁₇ represents a divalent organic group having from 1 to 90 carbon atoms. In the formula (3), X represents a single bond, a carbonyl group or a sulfonyl group (4), Y represents a divalent organic group having an aromatic ring or a divalent organic group having 1 to 20 carbon atoms. Represents an integer in the lower direction.)

The polyimide precursor according to the present invention is obtained by the following synthesis method. First, a tetracarboxylic acid dianhydride represented by at least one selected from the group consisting of the above-mentioned formulas (3) and (4) and an aliphatic diamine represented by the above formula (5) are polymerized and cyclized to obtain a polyimide , A tetracarboxylic acid dianhydride represented by at least one selected from the group consisting of the above formulas (3) and (4) and a diamine represented by the following formula (8) are polymerized to obtain a polyimide precursor .

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

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

(Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms 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, R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the above formula (3) or (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, Y represents a divalent organic group containing an aromatic ring or an aliphatic divalent organic group having 1 to 20 carbon atoms, and a is an integer of 1 or more and 20 or less 100, 0 <B <100, 0 <C <100, and 0 <A < 5? C / (A + B + C)? 0.95.

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

Examples of the tetracarboxylic acid dianhydride represented by the above formula (4) include ethylene glycol bis (trimellitic acid monoester acid anhydride) (hereinafter abbreviated as TMEG), p-phenylene bis (trimellitic acid monoester acid anhydride ), p-biphenylene bis (trimellitic acid monoester acid anhydride), m-phenylene bis (trimellitic acid monoester acid anhydride), o-phenylene bis (trimellitic acid monoester acid anhydride) 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 formula (5) is not limited as long as it has the structure represented by the formula (5), but a polyoxyethylenediamine compound such as 1,8-diamino-3,6-dioxioctane, Polyoxypropylene diamine compounds such as Zephamine D-230, D-400, D-2000 and D-4000, and polyoxypropylene diamine compounds such as HK -511, ED-600, ED-900, ED-2003, XTJ-542 and the like. The bending of the FPC after firing of the polyimide can be reduced by the skeleton having these oxyalkylene groups.

In the above formula (6), m, n and p each independently represent an integer of 0 or more and 100 or less. it is preferable that m + n + p> 5, more preferably m + n + p> 10. The polyimide precursor according to the present invention has a polyimide structure and a polyamic acid structure as repeating units. By introducing the diamine represented by the above formula (5) into the polyimide structure, the polyimide precursor varnish and the film The molecular weight is stabilized. When the diamine of the above 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 in comparison with the conventional polyamic acid, and the molecular weight is markedly lowered. By introducing the diamine represented by the above formula (5) into the polyimide structure, the molecular weight is stabilized without being influenced by the basicity of the aliphatic diamine.

Among the diamines represented by the above formula (5), diamines represented by the following formula (5-1) are more preferable from the viewpoint of reduction of the warp of the film.

(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).

R ₁₈ is preferably C ₂ H ₄ or C ₄ H _{8 in view} of developability and low water absorption. (M + n + p) from the viewpoint of suppressing the tackiness (stickiness) of the film and exhibiting flame retardancy, ) &Lt; / = 40. Among the above-mentioned formula (5-1), diamines represented by any one of the following formulas (5-2), (5-3) and (5-4) are particularly preferable. (5-3) corresponds to Jefamine ED-900, and the formula (5-4) corresponds to Jefamine XTJ-542 (all of Huntsman's Manufacturing).

(In the formulas (5-3) and (5-4), F and G satisfy F + G = 6.)

Examples of the diamines represented by the above formula (8) include 1,3-bis (4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) ) Alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'- , 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone (hereinafter abbreviated as DAS), 4,4'-diaminobenzamide, 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'-diaminobenzanilide, 1,3-bis (4-aminophenoxy) -2,2- , 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9- Bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) fluorene, Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene (hereinafter abbreviated as APB), 4,4'- Bis (4-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) propane (hereinafter abbreviated as BAPP), trimethylene- Aminophenyl) -4-aminobenzoate, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ Aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1-amino- 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 1,3-bis (4-aminophenoxybenzene) There. Of these, DAS, APB, BAPP and TMAB are preferable from the viewpoints of low Tg and developability of the polyimide precursor. These diamines may also be used as diamines of some polyimide syntheses.

Here, even when the polyimide precursor is used as a negative photosensitive resin composition, the polyimide precursor exhibits an effect even when used as a positive photosensitive resin composition. The polyimide precursor is not limited as long as it has a structure represented by the above formulas (1) and (2) as a constituent unit, but from the viewpoint of developability, a polyimide structure represented by the above formula (6) Is preferably a block copolymer having an amide acid structure as a repeating structural unit, and more preferably a block copolymer having a polyimide structure and a polyamic acid structure represented by the following formula (6-1) as repeating units .

(6-1), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and R ₁₇ represents a tetravalent organic group having 1 to 90 carbon atoms represents a divalent organic group, R ₁₈ is C ₂ H ₄ or C ₄ H _8, and, m, n, p are each independently an integer of not less than 0 40 12≤ (m + n + p) ≤40.)

Among the polyimide precursors represented by the above formula (6) including the polyimide precursor represented by the above formula (6) and the block copolymer represented by the formula (6-1), 0.1? C / (A + B C + (A + B + C) &amp;le; 0.9, more preferably a polyimide precursor satisfying 0.2 C / (A + B + C) Lt; = 0.75 is most preferable.

The tetracarboxylic dianhydride may include a tetracarboxylic dianhydride other than the above-mentioned formula (3) and the above formula (4) within a range not adversely affecting the performance.

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

Further, the content of the tetracarboxylic dianhydride is 50 parts by mass or less when 100 parts by mass of the tetracarboxylic acid dianhydride represented by the above formula (3) and the above formula (4) is taken as 100 parts by mass.

The main chain terminal of the polyimide precursor is not particularly limited as long as it does not affect the performance. The acid dianhydrides used for preparing the polyimide precursor, the terminal derived from the diamine, or the terminal may be sealed with other acid anhydrides, amine compounds or the like.

The weight average molecular weight of the polyimide precursor is preferably from 1,000 to 1,000,000. Here, the weight average molecular weight refers to the 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 1,000 or more from the viewpoint of the strength of the polyimide film, and is preferably 1000000 or less from the viewpoints of viscosity and moldability of the polyimide-containing resin composition. The weight average molecular weight is more preferably from 5000 to 500000, particularly preferably from 10000 to 300000, most preferably from 25000 to 50000.

A polyimide precursor having a polyimide structure and a polyamic acid structure as repeating units is obtained by a process (Step 1) of synthesizing a polyimide moiety in the first stage by reacting an acid dianhydride with a diamine in a non-equimolar amount, And the step of synthesizing the polyamide acid in the second step (step 2). Hereinafter, each step will be described.

(Step 1)

The step of synthesizing the polyimide moiety in the first step will be described. The step of synthesizing the polyimide moiety in the first step is not particularly limited, and a known method can be applied. More specifically, it is obtained by the following method. First, the diamine is dissolved and / or dispersed in a polymerization solvent, and an acid anhydride powder is added to the solution. Then, a solvent which is azeotropic 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 by using a mechanical stirrer. At this time, 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 moiety, the polyimide moiety can be synthesized either by adding a known imidization catalyst or by non-catalysis. Examples of imidization catalysts include, but are not limited to, acid anhydrides such as acetic anhydride,? -Valerolactone,? -Butyrolactone,? -Tetronic acid,? -Phthalide,? -Coumarin, Lactone compounds such as lead acid, and tertiary amines such as pyridine, quinoline, N-methylmorpholine and triethylamine. In addition, one kind or a mixture of two or more kinds may be used if necessary. Of these, a mixed system of? -Valerolactone and pyridine and a non-catalyst are particularly preferable in view of the height of reactivity and the effect on the next reaction.

The addition amount of the imidation catalyst is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, when 100 parts by mass of the polyamic acid is used.

Examples of the reaction solvent used for synthesizing the polyimide moiety include a reaction solvent having a carbon number such as dimethyl ether, diethyl ether, methyl ethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether An ether compound having 2 or more and 9 or less carbon atoms; Ketone compounds having 2 or more carbon atoms and 6 or less carbon atoms such as acetone and methyl ethyl ketone; Saturated hydrocarbon compounds having 5 or more carbon atoms and 10 or less carbon atoms such as n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane and decalin; Aromatic hydrocarbon compounds having 6 or more carbon atoms and 10 or less carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; Ester compounds having 3 or more carbon atoms and 12 or less carbon atoms such as methyl acetate, ethyl acetate,? -Butyrolactone and methyl benzoate; Halogenated compounds having 1 or more carbon atoms and 10 or less carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; Nitrogen-containing compounds having 2 or more carbon atoms and 10 or less carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; And sulfur compounds such as dimethyl sulfoxide. These may be used alone or as a mixture of two or more thereof. Particularly preferable solvents include ether compounds having 2 or more carbon atoms and 9 or less carbon atoms, ester compounds having 3 or more carbon atoms and 12 or less carbon atoms, aromatic hydrocarbon compounds having 6 or more carbon atoms and 10 or less carbon atoms, and nitrogenous compounds having 2 to 10 carbon atoms . These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like.

The synthesis of the polyimide moiety is preferably carried out at a reaction temperature of 15 ° C or higher and 250 ° C or lower. When the temperature is higher than 15 ° C, the reaction starts. When the temperature is lower than 250 ° C, the catalyst is not deactivated. Preferably 20 ° C or more and 220 ° C or less, more preferably 20 ° C or more and 200 ° C or less.

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

(Step 2)

Next, the step of synthesizing the polyamic acid moiety in the second step will be described. The synthesis of the polyamic acid moiety in the second step can be carried out by using the polyimide moiety obtained in Step 1 as a starting material and further adding a diamine and / or an acid anhydride to the mixture.

The polymerization temperature at the time of synthesizing the polyamic acid in the second step is preferably 0 ° C to 250 ° C, more preferably 0 ° C to 100 ° C, and particularly preferably 0 ° C to 80 ° C.

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

As the reaction solvent, the same solvent as used for the synthesis of the polyimide moiety in Step 1 may be used. In that case, the reaction solution of Step 1 can be used as it is. Further, a solvent other than that used for the synthesis of the polyimide moiety may be used.

Examples of such a solvent include ether compounds having 2 or more carbon atoms and 9 or less 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; Ketone compounds having 2 or more carbon atoms and 6 or less carbon atoms such as acetone and methyl ethyl ketone; Saturated hydrocarbon compounds having 5 or more carbon atoms and 10 or less carbon atoms such as n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane and decalin; Aromatic hydrocarbon compounds having 6 or more carbon atoms and 10 or less carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; Ester compounds having 3 or more carbon atoms and 12 or less carbon atoms such as methyl acetate, ethyl acetate,? -Butyrolactone and methyl benzoate; Halogenated compounds having 1 or more carbon atoms and 10 or less carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; Nitrogen-containing compounds having 2 or more carbon atoms and 10 or less carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; And sulfur compounds such as dimethyl sulfoxide.

These may be used alone or as a mixture of two or more thereof. Particularly preferable solvents include ether compounds having 2 or more carbon atoms and 9 or less carbon atoms, ester compounds having 3 or more carbon atoms and 12 or less carbon atoms, aromatic hydrocarbon compounds having 6 or more carbon atoms and 10 or less carbon atoms, and nitrogenous compounds having 2 to 10 carbon atoms . These can be arbitrarily selected in consideration of industrial productivity, influence on the next reaction, and the like.

The polyimide precursor after the completion of the production may be used while being dissolved in the reaction solvent, and recovered or purified by the following method.

The recovery of the polyimide precursor after the completion of the 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 dianhydrides and diamines in the reaction solution by filtration under reduced pressure, pressure filtration and the like. Further, a so-called reprecipitation method in which the reaction solution is added to a poor solvent and precipitated can be carried out. In addition, when a high purity polyimide precursor is required, an extraction method using a carbon dioxide supercritical system is also possible.

(B) Photosensitizer

The photosensitive resin composition according to the present invention contains the polyimide precursor and a photosensitizer. The photosensitive agent is a compound having a property that its structure is changed by light irradiation to change solubility in a solvent. Such a compound includes a so-called positive type in which a light irradiation site is dissolved and a so-called negative type in which a light irradiation site is insoluble.

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

(B-1) a (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, (Meth) acrylate, polyethylene glycol di (meth) acrylate, 2-di (p-toluenesulfonyl) di (meth) acrylate, (Meth) acrylate, trimethylolpropane tri (meth) acrylate, polyoxypropyl trimethylol propane tri (meth) acrylate, polyoxyethyl trimethylol propane tri (Meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylol propane triglycidyl ether (meth) acrylate, bisphenol A di (Meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta Di (meth) acrylate. Of 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. Further, a combination of a compound having two double bonds and a compound having three or more double bonds is preferable. When the amount of the polyimide precursor is 100 parts by mass, the amount of the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 10 parts by mass or less, More preferably not less than 40 parts by mass.

(C) a photopolymerization initiator

Examples of the photopolymerization initiator include benzyldimethylketalization such as 2,2-dimethoxy-1,2-diphenylethane-1-one, benzyl dipropyl ketaldehyde, benzyl diphenyl ketaldehyde, benzoin methyl ethers, Ether, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- , 2-fluorothioxanthone, 4-fluorothioxanthone, 2-chlorothioxanthone, 4-chlorothioxanthone, 1-chloro-4- propanedioxanthone, benzophenone, 4,4'-bis (Dimethylamino) benzophenone (Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 2,2-dimethoxy-2-phenylacetophenone, aromatic ketone compounds such as N-phenylglycine, Triarylimidazole dimer such as dimers, acridine compounds such as 9-phenylacridine,?,? -Dimethoxy-? -Morpholino-methylthiophenylacetophenone, 2,4,6- Trimethylbenzoyldiphenyl Oxime ester compounds such as benzoic acid, p-toluenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid, Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- Methyl-propan-1-one, 2-hydroxy-1- {4 - [(2-hydroxy- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2- (dimethylamino) Methylphenyl) methyl] -1- [4- (4-morphonyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethane Gt; 1- [9-ethyl Oxime esters such as 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime). Of these, oxime esters are preferable from the viewpoint of sensitivity.

The amount of the photopolymerization initiator is preferably 0.01 part by mass or more and 40 parts by mass or less from the viewpoint of sensitivity and resolution when the amount of the polyimide precursor is 100 parts by mass. More preferably 0.5 parts by mass or more and 35 parts by mass or less.

(B-2) a quinone diazide compound

Examples of the compound that exhibits positive photosensitivity include a compound containing a quinone diazide structure, an aromatic diazonium salt compound, and a compound having an azide structure. From the viewpoint of solubility contrast, a compound containing a quinone diazide structure is preferable.

Examples of the compound containing a quinone diazide structure include 1,2-benzoquinone diazidesulfonic acid esters, 1,2-benzoquinone diazidesulfonic acid amides, 1,2-naphthoquinone diazidesulfonic acid esters, 1,2 -Naphthoquinonediazidesulfonic acid amides can be mentioned. Specific examples thereof include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphtho Sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1 , 2-naphthoquinonediazide-5-sulfonic acid ester, and other 1,2-naphthoquinonediazidesulfonic acid esters of trihydroxybenzophenones; 2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2 -Naphthoquinonediazide-5-sulfonic acid ester, 2,2 ', 3', 4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, , 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- , 2-naphthoquinonediazide-4-sulfonic acid ester, 2,2 ', 3,4-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4'-tetrahydroxy-3'-methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone -1,2-naphthoquinonediamine De 5-a-tetrahydroxy benzophenones such as a sulfonic acid ester of 1,2-naphthoquinonediazide-sulfonic acid esters; 2,2 ', 3,4,6'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 3,4,6'-pentahydroxybenzophenone -1,2-naphthoquinonediazide-5-sulfonic acid ester, and the like; 1,2-naphthoquinonediazidesulfonic acid esters of pentahydroxybenzophenones; 2,3 ', 4,4', 5 ', 6', 4,4 ', 6,5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester -Hexahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3 ', 4,4', 5,5'-hexahydroxybenzophenone-1,2-naphthoquinone Diazide-4-sulfonic acid ester, and 3,3 ', 4,4', 5,5'-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester. 1,2-naphthoquinonediazidesulfonic acid esters of rhenium; Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide (P-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide Sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p- Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis Bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2'- 2-naphthoquinonediazide-4-sulfonic acid ester, 2,2'-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide- (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris -Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '- [1- [4- [1- [ ] -1- methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 4,4 '- [1- [4- [1- [ -1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane- (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-5-sulfonic acid ester Ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene-5,5', 6,6 ', 7,7'-hexanol-1,2-naphthoquinonedi Sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene-5,5', 6,6 ', 7,7'-hexanol- -Naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-2 ', 4', 7-trihydroxyplazane-1,2-naphthoquinonediazide- 1,2-naphthoquinonediazide-5-sulfonic acid esters such as 2,4-trimethyl-2 ', 4' And naphthoquinone diazidesulfonic acid esters. From the viewpoint of dissolution inhibiting ability, 1,2-naphthoquinonediazidesulfonic acid esters are preferable, and 1,2-naphthoquinonediazide-4-sulfonic acid esters, 1,2-naphthoquinonediazide-5 -Sulfonic acid esters are more preferable in terms of photosensitive contrast. Among them, compounds represented by the following formula (9) are particularly preferable.

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

As the photosensitizer, the compound b used in the following examples indicates that an average of 2.9 out of the three Qs in the above formula (9) has a structure represented by the above formula (10).

When the amount of the polyimide precursor is 100 parts by mass, 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 5 parts by mass or more 30 parts by mass or less. If it is 1 part by mass or more, dissolution inhibition of the unexposed portion tends to be sufficient, which is preferable. When the amount is less than 50 parts by mass, the sensitivity tends to be sufficiently high.

(D) a compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor

And a reactive 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 toughness, solvent resistance and heat resistance (thermal stability) of the film after firing.

Examples of the thermosetting resin include an epoxy resin, a cyanate ester resin, an unsaturated polyester resin, a benzoxazine resin, a benzoxazoline, a phenol resin, a melamine resin, a maleimide compound, and a block isocyanate.

Examples of the compound having reactivity with the polyimide precursor include a compound capable of forming a three-dimensional crosslinked structure by reacting with a carboxyl group, an amino group or an acid anhydride at the terminal of the polymer. Among them, a thermobase generating compound which generates an amino group as a base by heating is preferable. For example, by protecting with an acid chloride compound, which is protected by a dicarbonate compound exemplified by the formula (7), in which an amino group of a base compound such as an amine is formed with an acid such as a sulfonic acid.

(In the formula (7), R ₁₉ represents a divalent organic group having 1 to 20 carbon atoms and R ₂₀ represents a monovalent organic group having 1 to 20 carbon atoms.)

As a result, it is possible to obtain a thermal base generating agent which is stable at room temperature without developing basicity and is deprotected by heating to generate a base. The thermal base generator has an effect of improving the molecular weight of the polymer skeleton (extending the molecule) by reacting with the acid anhydride at the terminal in the polymer, and is effective for the alkali of TMAH (tetramethylammonium hydroxide) of the cured film And exhibits performance such as solvent resistance. From the viewpoint of solvent resistance and flame retardancy, a compound obtained by protecting the amino group of a base compound such as an amine with a dicarbonate compound exemplified by the above formula (7) is preferable as the thermal base generator, Advantageously, in view of manufacturing and solvent resistance, R ₁₉ is -Ar-Z-Ar-, -Ar- Z-Ar-Z-Ar- or -Ar-Z-Ar-Z- Ar-Z-Ar- , and , And Z is O or SO ₂ or C (CH ₃ ) ₂ . It is particularly preferable that R ₁₉ is -Ar-Z-Ar- or -Ar-Z-Ar-Z-Ar- and Z is O or SO ₂ (wherein Ar represents an aromatic ring). These are preferable in that the directional ring in the thermobilizer improves the compatibility by affinity with the aromatic ring of the anhydride of the acid represented by the formula (3) or the formula (4) constituting the polyimide precursor Do. In addition, it is presumed that the diamine after de-protection has a state of having an aromatic ring by having an aromatic ring in the thermobilizer, and that the amine is bonded between the polymers, so that the solvent resistance is expressed while imparting the bending resistance after firing . Particularly, when the diamine is used, the diamine having an aromatic ring and the acid of the formula (3) or the formula (4) having an aromatic ring may interact with the anhydride component, It is assumed that the coupling is facilitated. Further, it is preferable that R ₂₀ corresponding to the protecting group is an alkyl group having 2 to 10 carbon atoms, from the viewpoint that deprotection is easy. It is presumed that since the number of carbon atoms is from 2 to 10, it becomes possible to deprotect at a temperature lower than the temperature at which the polyimide precursor is baked.

The 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 preferably 50 parts by mass or less from the viewpoint of developing property when the amount of the polyimide precursor is 100 parts by mass, And more preferably not more than 1 part by mass.

(E)

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 phosphorus atom-containing compound. As such phosphorus compounds, phosphoric acid ester compounds, phosphazene compounds and the like can be given.

Examples of the phosphoric acid ester compound include phosphoric acid ester compounds having aliphatic hydrocarbon groups such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, triisobutyl phosphate and tris (2-ethylhexyl) phosphate as substituents, tris (butoxyethyl) phosphate A phosphoric acid ester compound having an aromatic organic group such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, resorcinol bis (diphenyl phosphate) as a substituent, a phosphoric acid ester compound having an aliphatic organic group containing an oxygen atom as a substituent, And the like. Among them, tris (butoxyethyl) phosphate and triisobutyl phosphate are preferable from the viewpoint of developability.

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

R ₂₁ , R ₂₂ , R ₂₃ and R ₂₄ in the phosphazene compound represented by the formula (11) and the formula (12) are not limited as long as they are organic groups having 1 to 20 carbon atoms and 20 or less carbon atoms. When the number of carbon atoms is 1 or more, flame retardancy tends to be manifested. If the carbon number is 20 or less, it is preferable because it tends to be compatible with the polyimide precursor. Of these, functional groups derived from an aromatic compound having 6 or more carbon atoms and 18 or less carbon atoms are particularly preferable from the viewpoint of flame retardancy. Examples of such functional groups include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, a 4-hydroxyphenyl group, a 2-cyanophenyl group, , A functional group having a phenyl group such as a 4-cyanophenyl group, a functional group having a naphthyl group such as a 1-naphthyl group and a 2-naphthyl group, a functional group having a naphthyl group such as a pyridine, imidazole, triazole or tetrazole Functional groups and the like. The compounds having these functional groups may be used singly or in combination of two or more as necessary. Of these, compounds having a phenyl group, a 3-methylphenyl group, a 4-hydroxyphenyl group and a 4-cyanophenyl group are preferable from the standpoint of availability.

The v in the phosphazene compound represented by the formula (11) is not limited as long as it is 3 or more and 25 or less. If it is 3 or more, flame retardancy is exhibited. If it is 25 or less, solubility in an organic solvent is high. Among them, v is preferably 3 or more and 10 or less in view of easy availability.

The w in the phosphazene compound represented by the formula (12) is not limited as long as it is 3 or more and 10,000 or less. If it is 3 or more, flame retardancy is exhibited. If it is 10000 or less, solubility in an organic solvent is high. Of these, in particular, from 3 to 100 are preferable from the viewpoint of availability.

D and E in the phosphazene compound represented by the formula (12) are not limited as long as they are organic groups having 3 to 30 carbon atoms. Among them, 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) and the like are preferable.

Examples _{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 , and -N═P (O) (OC ₆ H ₄ CN).

The phosphorus compounds may be used singly or in combination of two or more.

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

The photosensitive resin composition may contain other compounds within a range not adversely affecting its performance. Specific examples thereof include heterocyclic compounds for improving adhesion and pigments and dyes for coloring films.

The heterocyclic compound is not limited as long as it is a cyclic compound containing a hetero atom. Examples of the heteroatom include oxygen, sulfur, nitrogen and phosphorus. Specific examples of the heterocyclic compound include substituted imidazoles such as 2-methylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, 1,2- Imidazoles containing an aromatic group such as 1-benzyl-2-methylimidazole and 1-benzyl-2-phenylimidazole, imidazoles such as 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- (1 ', 2'-dicarboxyethylbenzotriazole), imidazole compounds such as imidazole-containing imidazole and imidazole silane-containing imidazole compounds such as 5-mercaptotriazole, Triazole compounds such as 1- (2-ethylhexylaminomethylbenzotriazole) and the like, and oxazole compounds such as 2-methyl-5-phenylbenzoxazole.

Examples of the pigment and dye include phthalocyanine compounds.

The addition amount of the other compounds is not limited as long as it is 0.01 parts by mass or more and 30 parts by mass or less. When the amount is more than 0.01 part by mass, the adhesiveness tends to improve sufficiently and the coloring property to the film tends to be improved. When the amount is less than 30 parts by mass, there is no adverse effect on photosensitivity. The photosensitive resin composition is optional and may 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 ether compounds having 2 or more carbon atoms and 9 or less 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 ; Ketone compounds having 2 or more carbon atoms and 6 or less carbon atoms such as acetone and methyl ethyl ketone; Saturated hydrocarbon compounds having 5 or more carbon atoms and 10 or less carbon atoms such as n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclohexane and decalin; Aromatic hydrocarbon compounds having 6 or more carbon atoms and 10 or less carbon atoms such as benzene, toluene, xylene, mesitylene, and tetralin; Ester compounds having 3 or more carbon atoms and 9 or less carbon atoms such as methyl acetate, ethyl acetate,? -Butyrolactone and methyl benzoate; Halogenated compounds having 1 or more carbon atoms and 10 or less carbon atoms such as chloroform, methylene chloride and 1,2-dichloroethane; Nitrogen-containing compounds having 2 or more carbon atoms and 10 or less carbon atoms such as acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; And sulfur compounds such as dimethyl sulfoxide.

These may be used alone or as a mixture of two or more thereof. Especially preferred examples of the organic solvent include an ether compound having 2 or more carbon atoms and 9 or less carbon atoms, an ester compound having 3 or more carbon atoms and 9 or less carbon atoms, an aromatic hydrocarbon compound having 6 to 10 carbon atoms and an aromatic hydrocarbon compound having 2 to 10 carbon atoms have.

If necessary, one kind or a mixture of two or more kinds may be used. From the viewpoint of solubility of the polyimide precursor, triethylene glycol dimethyl ether, N-methyl-2-pyrrolidone,? -Butyrolactone, N, N-dimethylformamide and N, N-dimethylacetamide are preferable.

The concentration of the polyimide precursor in the resin composition comprising the polyimide precursor and the organic solvent is not particularly limited as long as the concentration is such that the resin molded article can be synthesized. From the viewpoint of the film thickness of the resin molding to be produced, the concentration of the polyimide precursor is preferably not less than 1% by mass, and the concentration of the polyimide precursor is preferably 90% by mass or less in the uniformity of the film thickness of the resin molding. From the viewpoint of the film thickness of the obtained resin molded article, 2 mass% or more and 80 mass% or less is more preferable.

(F) Photosensitive film

The photosensitive resin composition according to the present invention can be suitably used as a photosensitive film. The photosensitive film according to the present invention comprises a support film as a substrate and the photosensitive resin composition formed on the support film. Further, in the photosensitive film according to the present invention, a carrier film may be formed on one surface side. Further, in the photosensitive film according to the present invention, in addition to these constitutions, a cover film may be provided.

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 is preferably 90% by mass or less from the viewpoints of viscosity and uniformity of the thickness of the photosensitive resin composition. From the viewpoint of the film thickness of the resulting photosensitive film, 2 mass% or more and 80 mass% or less is more preferable.

Next, a method for producing a photosensitive film will be described.

First, the photosensitive resin composition is coated on a substrate. The substrate is not limited as long as it is a substrate which is not damaged when forming the photosensitive dry film. Examples of such substrates include silicon wafers, glass, ceramics, heat-resistant resins, and carrier films. Examples of the carrier film include a polyethylene terephthalate film and a metal film. For reasons of handling, heat-resistant resins and carrier films are preferred, and polyethylene terephthalate films are particularly preferred from the standpoint of peelability after substrate bonding.

Examples of the coating method include bar coats, roller coats, die coats, blade coats, dip coats, doctor knives, spray coats, flow coats, spin coats, slit coats and brush coats. After the coating, a heat treatment referred to as pre-baking may be carried out by a hot plate or the like as necessary.

When a photosensitive film composed of a photosensitive resin composition is used, the solution of the photosensitive resin composition is applied on an arbitrary substrate by an arbitrary method, followed by drying to form a dry film, for example, a laminated film having a carrier film and a photosensitive film .

Further, it is also possible to form a laminated film by forming at least one cover film for arbitrary scattering or protection on the photosensitive film. In the laminated film according to the present invention, the cover film is not limited as long as it is a film for protecting a photosensitive film such as low-density polyethylene.

Subsequently, the photosensitive film is pressed onto the substrate having the wiring so as to cover the wiring, alkali development is performed, and baking is performed to obtain a flexible printed wiring board.

Examples of the substrate having the wiring in the flexible printed wiring board include a hard substrate such as a glass epoxy substrate or a glass-ceramid substrate, or a flexible substrate such as a copper-clad laminate. Of these, a flexible substrate is preferable from the viewpoint of bending capability.

The method for forming the flexible printed wiring board is not limited as long as the photosensitive film is formed on the substrate so as to cover the wiring. Examples of such a forming method include a method of performing a thermal press, a thermal laminate, a thermal vacuum press, a thermal vacuum laminate and the like while the photosensitive film according to the present invention is in contact with the wiring side of the substrate having the wiring. Among them, a thermal vacuum press and a thermal vacuum laminate are preferable from the viewpoint of embedding a photosensitive film between wirings.

The heating temperature at the time of laminating the photosensitive film on the substrate having the wiring is not limited as far as it is a temperature at which the photosensitive film can adhere to the substrate. From the viewpoint of adhesion to the substrate or from the viewpoint of decomposition or side reaction of the photosensitive film, it is preferable to be not less than 30 ° C and not more than 400 ° C. More preferably 50 ° C or more and 150 ° C or less.

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

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

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

Subsequently, the printed wiring board pressing the photosensitive film is fired to form a printed wiring board. The firing is preferably carried out at a temperature of 30 占 폚 or higher and 400 占 폚 or lower from the viewpoint of solvent removal or side reaction or decomposition. More preferably not lower than 100 ° C but not higher than 300 ° C.

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

The polyimide precursor and the photosensitive resin composition according to the present invention exhibit good warpage after curing and good developing properties and exhibit chemical resistance when formed into a cured product. Therefore, in the field of electronic devices, A protection layer of a circuit board, an insulating layer formation of a laminated board, a silicon wafer used for a semiconductor device, a semiconductor chip, a member around the semiconductor device, a semiconductor mounting board, a heat sink, a lead pin, And is used for forming a film on electronic parts for use in bonding. Thus, the protective film for protecting the wirings formed on the silicon wafer, the copper-clad laminate, the printed wiring board, and the like is referred to as a cover-lay.

The resin composition according to the present invention may be a cover or a flexible printed wiring board by imidization. Alternatively, a cover layer obtained by imidizing the resin composition according to the present invention on a copper-clad laminate may be provided as a laminate.

The polyimide precursor and the photosensitive resin composition according to the present invention can be used as substrates for flexible printed wiring circuits (FPC), substrates for tape automation bonding (TAB), substrates for liquid crystal displays and electric insulating films in various electronic devices, It can be suitably used for a substrate for a luminescence (EL) display, a substrate for an electronic paper, a substrate for a solar cell, particularly a coverlay for a flexible printed wiring circuit.

[Example]

Next, the following description will be made on the basis of embodiments for clarifying the effects of the present invention. On the other hand, the present invention is not limited in any way by the following examples.

<Reagent>

In the following Examples and Comparative Examples, the reagents used were TMEG (trade name: TMEG-100 (manufactured by Shin-Nihon Rika KK), BTDA (manufactured by Daicel Kagaku), BPDA (manufactured by Mitsui Chemicals) APB-N (manufactured by Mitsui Kagaku), DAS (manufactured by Huntsman Corporation), BAPP (manufactured by Wakayama Seikako Co., Ltd.), APB (trade name: (Trade name: Jeffamine XX-J-542, manufactured by Huntsman), Jeffamine (Jeffamine ED-900, Huntsman Inc.), Jeffamine (Jeffamine D-2000, (Manufactured by Wako Pure Chemical Industries, Ltd.), anhydrous nadic acid (manufactured by Hitachi Chemical Co., Ltd.), a phosphazene compound (trade name: FP-390, manufactured by Fushimi Chemical Industries, Ltd.), a phosphazene compound Block isocyanate (trade name: TPA-B80E, manufactured by Asahi Kasei Chemicals Co., Ltd.), block isocyanate (trade name: SBN-7 (Trade name: BPA-500, manufactured by Shin Nakamura Kagaku Co., Ltd.) was used as a polyol (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.), one end block isocyanate (trade name: CALENS MOI-BP, manufactured by Showa Denko K.K.), EO modified bisphenol A dimethacrylate 9-ethyl-6- (2-methylbenzoyl) -9H-carbazole (trade name: Aronix M-306, manufactured by Toagosei Co., Ltd.), pentaerythritol tri / tetra 3-yl] -1- (O-acetyloxime) (trade name: IRGACURE OXE 02, manufactured by Ciba GeFan Company), toluene (manufactured by Wako Pure Chemical Industries, Ltd. for organic synthesis), γ-butyrolactone (Manufactured by Wako Pure Chemical Industries, Ltd.), sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), 1,2-naphthoquinone diazide-5-sulfonic acid ester (trade name: PA- , The above-mentioned compound b (see the above formulas (9) and (10)) can be subjected to a reaction without any special purification He said.

&Lt; Measurement of weight average molecular weight &

The weight average molecular weight was measured by Gel Permeation Chromatography (GPC) under the following conditions. 24.8 mmol / L lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity: 99.5%) and 63.2 g of sodium chloride were added to the solution before measurement, using N, N-dimethylformamide (manufactured by Wako Pure Chemical Industries, mmol / L phosphoric acid (manufactured by Wako Pure Chemical Industries, Ltd., for high-performance liquid chromatography) was added.

Column: Shodex KD-806M (manufactured by Showa Denko K.K.)

Flow rate: 1.0 mL / min

Column temperature: 40 ° C

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)

UV-2075Plus (UV-VIS: absorptiometer at exothermy, manufactured by JASCO)

The calibration curve for calculating the weight average molecular weight was prepared using standard polystyrene (manufactured by Toso Co., Ltd.).

&Lt; Measurement of film thickness &

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

<Dry Film Production Method>

The dry film was produced by coating a PET film (N152Q, manufactured by Teijin DuPont Films Japan Limited) with a photosensitive resin composition as a base. The coating of the photosensitive resin composition was carried out by a doctor blade method using a FILMCOATER (PI1210, manufactured by TESTER SANGYO). The above-mentioned photosensitive resin composition was dropped onto the PET film, and the coating was performed with a clearance of 150 mu m. The coated film was dried at 95 캜 for 30 minutes using a drier (SPHH-10l, manufactured by ESPEC) to obtain a photosensitive dry film.

<Tackiness evaluation>

The presence or absence of the tack of the photosensitive layer after drying at 95 캜 for 30 minutes was evaluated by palpation. The fingerprints were marked as ×, and the fingerprints were not marked.

&Lt; Lamination condition &gt;

The lamination was carried out using a vacuum press machine (manufactured by Meikisha Sekusho Co., Ltd.). A press temperature of 70 占 폚, a press pressure of 0.5 MPa, and a press time of 30 seconds.

<Evaluation of Developability>

The developability was evaluated by an optical microscope under the following conditions. After laminating on the copper-clad laminate using the photosensitive dry film under the above-described lamination conditions, in the case of the positive photosensitive resin composition, exposure was carried out at a dose of 1.0 J / cm 2 using a positive mask and the negative photosensitive resin In the case of the composition, exposure was performed at 30 to 270 mJ / cm 2. Then, alkali developing treatment with an aqueous solution of sodium carbonate and rinsing with water were carried out, and the pattern after drying was evaluated with an optical microscope. A circular pattern of 100 μm diameter (interval of 100 μm pitch) was used for the mask. A case where the copper surface appeared in the exposed portion due to the development and the remaining film ratio was 75% or more was rated as?, And the case where the other resolutions were poor or the film thickness was less than 75% was evaluated as?.

<Measurement of warpage after firing>

The obtained photosensitive dry film was laminated to Capton (registered trademark) under the above lamination conditions, and then baked at 120 ° C for 1 hour and then at 180 ° C for 1 hour. The sintered film was cut into 5 cm squares, and those having a flying height of 10 mm or less at the end portion were evaluated as &amp; cir &amp;

&Lt; Bending test after firing &gt;

The film obtained after the firing (curing) was observed by observing by visually confirming cracking and peeling of the cover film by folding (folding) at 180 degrees. A case where no cracking or peeling was observed was evaluated as &amp; cir &amp;

<Evaluation of solvent resistance>

The solvent resistance was evaluated by the residual film ratio under the following measurement conditions. The film obtained after curing was cut into 5 cm squares and immersed in a 2.38 mass% TMAH solution at 50 占 폚 for 2 minutes to measure the residual film ratio from the film thickness before and after immersion.

&Lt; Evaluation of flame retardancy &

The flame retardancy was evaluated by a flame retardancy test under the following conditions. The photosensitive dry film was laminated on the polyimide film (Kapton EN-100, trade name, manufactured by Torre-DuPont) under the above lamination conditions, and then baked at 120 ° C for 1 hour and then at 180 ° C for 1 hour.

The obtained film was cut to a width of 1 cm and a length of 5 cm. Then, a process of burning one end of the test piece by burning was visually observed and confirmed. A specimen which had been extinguished during the course was rated as O, and a specimen which was burned in all was evaluated as X.

&Lt; Evaluation of thermal stability &

The thermal stability was evaluated by the rate of change of the weight average molecular weight of the polyimide precursor before and after coating. The polyimide precursor was prepared by the dry film production method described above, and the obtained dry film was dissolved in the GPC measurement solvent, and the weight average molecular weight was measured by GPC. The obtained weight average molecular weight was determined by dissolving the polyimide precursor solution before coating drying in the above GPC measurement solvent and determining the rate of change from the weight average molecular weight by GPC measured.

&Lt; IR spectrum measurement &gt;

The IR spectrum was measured by the following conditions. The polyimide resin precursor and / or photosensitive resin composition was coated on the copper foil using a hand coater so that the film thickness after drying was 17 占 퐉, and the coated sample was dried in a dryer at 95 占 폚 for 30 minutes. IR spectra of the obtained film were measured by an ATR method and / or a transmission method using an infrared spectrophotometer (FT / IR-460Puls, manufactured by Nippon Bunko).

<Glass transition temperature: Tg>

The glass transition temperature was measured using a thermomechanical analyzer (TMA-50, manufactured by Shimadzu Corporation). Test piece elongation was measured by thermomechanical analysis in a range of a load of 5 g, a temperature raising rate of 10 占 폚 / min, a nitrogen atmosphere (flow rate: 20 ml / min) and a temperature of 50 to 450 占 폚, To determine the glass transition temperature of the polyimide film.

(Synthesis Example 1) Synthesis of thermal base generating agent 1

Under a nitrogen atmosphere, a 2 L isostatic dropping funnel was installed in a 18 L hollow tank and degassed. Thereafter, tetrahydrofuran (1683 g) and 3,4'-oxydianiline (3 mol) were added to the tank in an 18 L tank, and di-t-butyl (6.2 mol) dianhydride in tetrahydrofuran A solution diluted with furan (1000 g) was added. This solution was added dropwise to the 18 L tank over 165 minutes so that the internal temperature in the tank was 22 DEG C or lower. Thereafter, the reaction was carried out at 50 DEG C for 21 hours with stirring. Thereafter, ion-exchanged water (4.8 L) and ethyl acetate (3.6 L) were added to a 30 L extractor to carry out extraction and separation to obtain a reddish brown transparent organic layer. The organic layer was distilled off with a 50 L evaporator. The residue was crystallized from hexane (3.6 L) and ethanol (360 ml), filtered, and then vacuum-dried to obtain a hot base generating agent 1 represented by the following chemical formula (13) as a pale brown solid .

The results of the IR spectrum of the thermobase generator 1 as measured by the above IR spectrometry are shown in Fig. 1, and the appearance positions of the peaks are 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) Synthesis of thermal base generating agent 2

A thermobase generator 2 was obtained according to the method described in Synthesis Example 1, except that APB was used as the diamine in Synthesis Example 1.

(Synthesis Example 3) Synthesis of thermal nucleophilic agent 3

In the same manner as in Synthesis Example 1 except that DAS was used as the diamine, the thermal base generating agent 3 was obtained according to the method described in Synthesis Example 1.

[Example 1]

(18.6 mmol), gamma -butyrolactone (60 g), 5BTA (60 mmol) were added to a separable flask equipped with a Dean-Stark apparatus and a reflux condenser under a nitrogen atmosphere. ) And toluene (75 g), and the mixture was heated and stirred at 50 占 폚 for 1 hour. Subsequently, the mixture was heated and stirred at 180 占 폚 for 2 hours. After removing the azeotropic solvent toluene over 2.5 hours, the reaction mixture was cooled to 25 占 폚. Subsequently, APB-N (37.2 mmol) and? -Butyrolactone (45.6 g) were added and stirred at 70 占 폚 for 5 hours to obtain a? -Butyrolactone solution of the polyimide precursor (1). The results of evaluation of the weight average molecular weight and the thermal stability of the polyimide precursor (1) are shown in Table 1 below.

The IR spectrum of the polyimide precursor (1) measured by the IR spectrum measurement method is shown in FIG. 2, and the appearance position of the peak is shown below.

Peak appearance position (cm ^-1 ): 2941, 2866, 1780, 1719, 1594, 1542, 1480, 1438, 1376, 1288, 1249, 1179, 1111, 987, 864, 731

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

Subsequently, BPE-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-390 (40 parts by mass) were added to 100 parts by mass of the polyimide precursor And mixed to prepare a photosensitive resin composition (1).

The photosensitive resin composition (1) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 3%.

[Example 2]

A photosensitive resin composition (2) was prepared in the same manner as in Example 1 except that FP-300 was used instead of FP-390 as the phosphazene compound.

The photosensitive resin composition (2) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 4%.

[Example 3]

(6.2 mmol),? -Butyrolactone (30 g), 5BTA (20 mmol), and toluene (25 g) were charged in a 500 mL separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. (4.8 mmol) and γ-valerolactone (2.4 mmol) were added as an imidation catalyst and the mixture was heated and stirred at 140 ° C. for 6 hours under a nitrogen stream (400 mL / min) to remove the azeotropic solvent toluene and the catalyst did. The reaction solution was cooled to 25 占 폚 and then APB-N (12.4 mmol) and? -Butyrolactone (5.2 g) were added and stirred at 70 占 폚 for 5 hours to obtain? -Butyrolactone Solution. The results of the weight average molecular weight and the thermal stability evaluation of the polyimide precursor (2) 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-390 (40 parts by mass) were mixed with 100 parts by mass of the polyimide precursor To prepare a photosensitive resin composition (3).

The photosensitive resin composition (3) was evaluated for alkali developability in a 1% by mass aqueous sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 3%.

[Example 4]

Under a nitrogen atmosphere, γ-butyrolactone (42.0 g), triethylene glycol dimethyl ether (18.0 g), toluene (20.0 g) and Zephamin XTJ-542 (18.85 mmol) were charged in a separable flask equipped with a Dean- ) And 5BTA (60.0 mmol) were charged, and 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, APB-N (37.2 mmol) was added thereto, and the mixture was stirred at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (3). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (3) are shown in Table 1 below.

The results of the IR spectrum of the polyimide precursor (3) measured by the above IR spectrometry method are shown in Fig. 3, and the appearance positions of the peaks are shown below.

(Cm ^-1 ): 2936, 2868, 1773, 1717, 1595, 1543, 1480, 1438, 1373, 1247, 1180, 1154, 1105, 989, 861, 731

BP-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-390 (40 parts by mass) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (4).

The photosensitive resin composition (4) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 4%.

[Example 5]

Under a nitrogen atmosphere, γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g) and Zephamin XTJ-542 (14.85 mmol) were charged in a separable flask equipped with a Dean- ) And TMEG (39.0 mmol) were charged, and 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, APB-N (21.41 mmol) was added, and the mixture was stirred at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (4). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (4) 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-390 (40 parts by mass) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (5).

The photosensitive resin composition (5) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 2%.

[Example 6]

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

The photosensitive resin composition (6) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 2%.

[Example 7]

A polyimide precursor (5) was obtained in the same manner as in Example 5 except that the diamine was replaced by Zephamine XTJ-542 (trade name: Zephamine ED-900 (Huntsman)) as a diamine. . The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (5) are shown in Table 1 below.

A photosensitive resin composition (7) was prepared in the same manner as in Example 5. The photosensitive resin composition (7) was evaluated for alkali developability in a 1 mass% sodium carbonate aqueous solution with respect to 1 mass% sodium carbonate, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film and glass transition temperature measurement . The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 2%.

[Example 8]

A polyimide precursor (6) was obtained in the same manner as in Example 5, except that the diamine was replaced with Zephamine XTJ-542 (trade name: Zephamine D-2000, manufactured by Huntsman) . The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (6) are shown in Table 1 below.

A photosensitive resin composition (8) was prepared in the same manner as in Example 5. The photosensitive resin composition (8) was evaluated for alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 2%.

[Example 9]

Under a nitrogen atmosphere, γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g) and Zephamin XTJ-542 (10 mmol) were charged in a separable flask equipped with a Dean- ) And TMEG (39.0 mmol) were charged, and the temperature was raised to 180 ° C and the mixture was heated and stirred at 180 ° C for 1 hour. After the toluene as an azeotropic solvent was removed, the solution was cooled to 25 ° C, followed by addition of APB-N (21.41 mmol) and stirring at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (7). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (7) 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-390 (40 parts by mass) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (9).

The photosensitive resin composition (9) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 2%.

[Example 10]

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

(30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass), FP-390 (40 parts by mass), TPA- And B80E (5 parts by mass) were mixed to prepare a photosensitive resin composition (10).

The photosensitive resin composition (10) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 15%.

[Example 11]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), and Zephamin XTJ-542 (12.4 mmol) were added to a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ) And BPDA (47.58 mmol) were charged, 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, APB-N (31.13 mmol) was added thereto, and the mixture was stirred at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (9). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (9) are shown in Table 1 below.

BP-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-390 (40 parts by mass) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (11).

The photosensitive resin composition (11) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 30%.

The results of IR spectroscopy of the photosensitive resin composition after calcination as measured by the IR spectrum measurement method are shown in Fig. 4, and the appearance positions of the peaks are shown below.

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

[Example 12]

A photosensitive resin composition (12) was prepared in the same manner as in Example 11 except that FP-300 was used instead of FP-390 as the phosphazene compound.

The photosensitive resin composition (12) was evaluated for alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 25%.

[Example 13]

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 in Example 11.

The photosensitive resin composition (13) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 50%.

[Example 14]

A photosensitive resin composition (14) was prepared in the same manner as in Example 12 except that TPA-B80E (5 parts by mass) was further mixed.

The photosensitive resin composition (14) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 55%.

[Example 15]

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 in Example 12.

The photosensitive resin composition (15) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 60%.

[Example 16]

A photosensitive resin composition (16) was prepared according to the method described in Example 11 except that the car lens MOI-BP (5 parts by mass) was further used in Example 12.

The photosensitive resin composition (16) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 58%.

[Example 17]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), and Zephamin XTJ-542 (16.9 mmol) were charged in a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ) And BPDA (47.58 mmol) were charged, the temperature was raised to 180 ° C, and the mixture was heated and stirred at 180 ° C for 1 hour. After the toluene as the azeotropic solvent was removed, the solution was cooled to 25 deg. C, followed by addition of DAS (25.08 mmol) and stirring at 25 deg. C for 8 hours to obtain a solution of the polyimide precursor (10). The weight average molecular weight, C / (A + B + C), and the results of the evaluation of the thermal stability of the polyimide precursor 10 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) were mixed with 100 parts by mass of the polyimide precursor , And a photosensitive resin composition (17) were prepared.

The photosensitive resin composition (17) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 65%.

[Example 18]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g) and Zephamin XTJ-542 (12.4 mmol) were added to a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ), BPDA (31.72 mmol) and ODPA (15.86 mmol) were placed, heated to 180 ° C, and heated and stirred at 180 ° C for 1 hour. After removing toluene as an azeotropic solvent, the solution was cooled to 25 ° C, APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (11). The weight average molecular weight, C / (A + B + C), and the results of the evaluation of the thermal stability of the polyimide precursor (11) 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) were mixed with 100 parts by mass of the polyimide precursor To prepare a photosensitive resin composition (18).

The photosensitive resin composition (18) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. The solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 63%.

[Example 19]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), and Zephamin XTJ-542 (16.9 mmol) were charged in a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ), BPDA (31.72 mmol) and ODPA (15.86 mmol) were placed, heated to 180 ° C, and heated and stirred at 180 ° C for 1 hour. After the toluene as an azeotropic solvent was removed, the solution was cooled to 25 占 폚, DAS (25.08 mmol) was added, and the mixture was stirred at 25 占 폚 for 8 hours to obtain a solution of the polyimide precursor (12). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor 12 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) were mixed with 100 parts by mass of the polyimide precursor To prepare a photosensitive resin composition (19).

The photosensitive resin composition (19) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. The solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 70%.

[Example 20]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), and Zephamin XTJ-542 (12.4 mmol) were added to a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ), BPDA (44.0 mmol) and maleic anhydride (3.58 mmol) were charged, heated to 180 ° C, and heated and stirred at 180 ° C for 1 hour. After the toluene as the azeotropic solvent was removed, the solution was cooled to 25 ° C, APB-N (31.13 mmol) was added, and the mixture was stirred at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (13). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (13) 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) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (20).

Evaluation of alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, measurement of bowing of the film after firing, and measurement of glass transition temperature were performed on the photosensitive resin composition (20). The results are shown in Table 2 below. The solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 27%.

[Example 21]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), and Zephamin XTJ-542 (12.4 mmol) were added to a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ), BPDA (44.0 mmol) and anhydrous nadic acid (3.58 mmol) were charged, the temperature was raised to 180 ° C, and the mixture was heated and stirred at 180 ° C for 1 hour. After the toluene as an azeotropic solvent was removed, the solution was cooled to 25 占 폚, APB-N (31.13 mmol) was added, and the mixture was stirred at 25 占 폚 for 8 hours to obtain a solution of the polyimide precursor. The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor 14 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) were mixed with 100 parts by mass of the polyimide precursor To prepare a photosensitive resin composition (21).

The photosensitive resin composition (21) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 28%.

[Example 22]

(35.0 g), triethylene glycol dimethyl ether (15.0 g), toluene (20.0 g), and Zephamin XTJ-542 (16.9 mmol) were charged in a separable flask equipped with a Dean Stark apparatus and a reflux condenser under a nitrogen atmosphere. ), BPDA (44.0 mmol) and maleic anhydride (3.58 mmol) were charged, heated to 180 ° C, and heated and stirred at 180 ° C for 1 hour. After removing toluene as an azeotropic solvent, the solution was cooled to 25 占 폚, DAS (25.08 mmol) was added, and the mixture was stirred at 25 占 폚 for 8 hours to obtain a solution of the polyimide precursor (15). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (15) 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) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (22).

The photosensitive resin composition (22) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 26%.

[Example 23]

Under a nitrogen atmosphere, γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g) and Zephamin XTJ-542 (16.0 mmol) were charged in a separable flask equipped with a Dean- ) And TMEG (39.0 mmol) were charged, the temperature was raised to 180 ° C, and the mixture was heated and stirred at 180 ° C for 1 hour. After the toluene as an azeotropic solvent was removed, the solution was cooled to 25 占 폚, followed by BAPP (19.49 mmol) and stirred at 25 占 폚 for 8 hours to obtain a solution of the polyimide precursor (16). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor 16 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) were mixed with 100 parts by mass of the polyimide precursor To prepare a photosensitive resin composition (23).

The photosensitive resin composition (23) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 4%.

[Example 24]

Under a nitrogen atmosphere, γ-butyrolactone (49.0 g), triethylene glycol dimethyl ether (21.0 g), toluene (20.0 g) and Zephamin XTJ-542 (10.4 mmol) were charged in a separable flask equipped with a Dean- ) And TMEG (39.0 mmol) were charged, and the temperature was raised to 180 ° C and the mixture was heated and stirred at 180 ° C for 1 hour. After the toluene as an azeotropic solvent was removed, the solution was cooled to 25 ° C, followed by addition of TMAB (25.13 mmol) and stirring at 25 ° C for 8 hours to obtain a solution of the polyimide precursor (17). The weight average molecular weight, C / (A + B + C) and the results of the evaluation of the thermal stability of the polyimide precursor (17) 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) were mixed with 100 parts by mass of polyimide precursor To prepare a photosensitive resin composition (24).

The photosensitive resin composition (24) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, film warpage measurement after firing, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 3%.

[Example 25]

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor (1) (25) was prepared.

The photosensitive resin composition (25) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 3%.

[Example 26]

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor (3) obtained in Example 4 to obtain a photosensitive resin composition (26).

The photosensitive resin composition (26) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 4%.

[Example 27]

2-naphthoquinonediazide-5-sulfonic acid ester (PA6) (20 parts by mass) was mixed with 100 parts by mass of the polyimide precursor (1) obtained in Example 1 to obtain a photosensitive resin composition (27) It was prepared.

The photosensitive resin composition (27) was evaluated for alkaline developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 68%.

[Example 28]

BP-500 (30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-390 (40 parts by mass) were added to 100 parts by mass of the polyimide precursor (5 parts by mass) were mixed to prepare a photosensitive resin composition (28).

The photosensitive resin composition (28) was evaluated for alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, and warpage measurement of the fired film. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 95%.

[Example 29]

A photosensitive resin composition (29) was prepared in accordance with the method described in Example 28 except that the thermobase generator (2) was used instead of the thermobase generator (1).

The photosensitive resin composition (29) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 90%.

[Example 30]

A photosensitive resin composition (30) was prepared in accordance with the method described in Example 28 except that the thermobase generator (3) was used instead of the thermobase generator (1).

The photosensitive resin composition (30) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 94%.

[Example 31]

(30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-300 (40 parts by mass) were added to 100 parts by mass of the polyimide precursor (9) (5 parts by mass) were mixed to prepare a photosensitive resin composition (31).

The photosensitive resin composition (31) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, and warpage measurement of the fired film. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 98%.

[Example 32]

A photosensitive resin composition (32) was prepared in the same manner as in Example 31, except that the thermobase generator (2) was used instead of the thermobase generator (1).

The photosensitive resin composition (32) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 94%.

[Example 33]

A photosensitive resin composition (33) was prepared in the same manner as in Example 31, except that the heat-generating group-generating compound (3) was used instead of the heat-generating group-generating compound (1).

The photosensitive resin composition (33) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 95%.

[Example 34]

(30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-300 (40 parts by mass) were added to 100 parts by mass of the polyimide precursor (13) (5 parts by mass) were mixed to prepare a photosensitive resin composition (34).

The photosensitive resin composition (34) was evaluated for alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, and warpage measurement of the fired film. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 81%.

[Example 35]

A photosensitive resin composition (35) was prepared in the same manner as in Example 34, except that the heat-generating base generator (2) was used instead of the heat-generating base generator (1).

The photosensitive resin composition (35) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 80%.

[Example 36]

A photosensitive resin composition (36) was prepared in the same manner as in Example 34, except that the heat-generating group-generating agent (3) was used instead of the heat-generating group-generating agent (1).

The photosensitive resin composition (36) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 80%.

[Example 37]

(30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-300 (40 parts by mass) were added to 100 parts by mass of the polyimide precursor (14) (5 parts by mass) were mixed to prepare a photosensitive resin composition (37).

The photosensitive resin composition (37) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, and warpage measurement of the fired film. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 84%.

[Example 38]

A photosensitive resin composition (38) was prepared in accordance with the method described in Example 37 except that the thermobase generator (2) was used instead of the thermobase generator (1).

The photosensitive resin composition (38) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 82%.

[Example 39]

A photosensitive resin composition (39) was prepared in the same manner as in Example 37, except that the thermobase generator (3) was used instead of the thermobase generator (1).

The photosensitive resin composition (39) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 83%.

[Example 40]

BP-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) were added to 100 parts by mass of the polyimide precursor (5 parts by mass) were mixed to prepare a photosensitive resin composition (40).

The photosensitive resin composition (40) was evaluated for alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, and warpage measurement of the fired film. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 82%.

[Example 41]

A photosensitive resin composition (41) was prepared in the same manner as in Example 40, except that the thermal base generator 2 was used instead of the thermal base generator 1.

The photosensitive resin composition (41) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 81%.

[Example 42]

A photosensitive resin composition (42) was prepared in accordance with the method described in Example 40, except that the thermal base generator 3 was used in place of the thermal base generator 1 in Example 40.

The photosensitive resin composition (42) was evaluated for alkalinity developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 80%.

[Example 43]

(30 parts by mass), M-306 (10 parts by mass), IRGACURE OXE 02 (1 part by mass) and FP-300 (40 parts by mass) were added to 100 parts by mass of the polyimide precursor (15) (5 parts by mass) were mixed to prepare a photosensitive resin composition (43).

The photosensitive resin composition (43) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, and warpage measurement of the fired film. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 86%.

[Example 44]

A photosensitive resin composition (44) was prepared in the same manner as in Example 43, except that the thermobase generator (2) was used instead of the thermobase generator (1).

Evaluation of alkali developability in a 1 mass% sodium carbonate aqueous solution, tackiness, bending test after firing, flame resistance test, warp of the film after firing, and glass transition temperature were measured for the photosensitive resin composition (44). The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 85%.

[Example 45]

A photosensitive resin composition (45) was prepared in the same manner as in Example 44, except that the thermobase generator (3) was used instead of the thermobase generator (1).

The photosensitive resin composition (45) was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 84%.

[Comparative Example 1]

(4.45 mmol),? -Butyrolactone (32.5 g), APB-N (9.05 mmol) and 5-BTA (15 mmol) were placed in a separable flask under a nitrogen atmosphere, The temperature was gradually raised, and the mixture was heated and stirred at 60 占 폚 for 3 hours. The mixture was heated and stirred at 70 DEG C for 1 hour to obtain a solution of a polyimide precursor of gamma -butyrolactone. The weight average molecular weight, C / (A + B + C), and the results of the evaluation of the thermal stability of the polyimide precursor of Comparative Example 1 are shown in Table 1 below.

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 1 to obtain a photosensitive resin composition .

The photosensitive resin composition of Comparative Example 1 was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 32%.

[Comparative Example 2]

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

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 2 to obtain a photosensitive resin composition .

The photosensitive resin composition of Comparative Example 2 was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 52%.

[Comparative Example 3]

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

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 3 to obtain a photosensitive resin composition .

The photosensitive resin composition of Comparative Example 3 was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance of the obtained film after the firing was evaluated with respect to the TMAH solution, and the residual film ratio was 15%.

[Comparative Example 4]

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

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 4 to obtain a photosensitive resin composition .

The photosensitive resin composition of Comparative Example 4 was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 61%.

[Comparative Example 5]

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

BPE-500 (30 parts by mass), M-306 (10 parts by mass) and IRGACURE OXE 02 (1 part by mass) were mixed with 100 parts by mass of the polyimide precursor of Comparative Example 5 to obtain a photosensitive resin composition .

The photosensitive resin composition of Comparative Example 5 was evaluated for alkali developability in an aqueous 1% by mass sodium carbonate solution, tackiness, bending test after firing, flame resistance test, warpage measurement of the fired film, and glass transition temperature measurement. The results are shown in Table 2 below. Further, the solvent resistance to the TMAH solution of the obtained film after the firing was evaluated, and the residual film ratio was 2%.

As can be seen from the results of Tables 1 and 2, the polyimide precursor (Example 45 to Example 45) had a weight-average molecular weight lowered at 95 占 폚 when compared with Comparative Example 5 The heat stability, the bending test, the flame retardancy, the warpage, the developability, the tackiness and the solvent resistance are good.

In particular, as can be seen from Example 45 in Example 28, in the case of using the thermobase generator 3 in the thermobase generator 1 having a specific structure, the residual film ratio is greatly increased, . This is believed to be due to the interaction between the diamine having an aromatic ring generated by pyrolysis and the polyimide precursor having an aromatic ring as described above. Further, as can be seen from Comparative Example 5, when the diamine having a specific structure is not contained in the polyimide structure, the thermal stability, the bending test, the flame retardancy, the developability and the tactility are deteriorated.

The polyimide precursor can be suitably used as a surface protective film of a semiconductor device, an interlayer insulating film and an insulating film for rewiring, a protective film of a device having a bump structure, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper foil and a liquid crystal alignment film.

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

Claims (18)

A polyimide precursor having a polyimide structure represented by the following formula (1) and a polyamic acid structure represented by the following formula (2) as repeating units, wherein the tetracarboxylic acid dianhydride constituting the polyimide precursor is , At least one tetracarboxylic acid dianhydride selected from the group consisting of the following formula (3) and the following formula (4), and the diamine constituting the polyimide structure includes a diamine represented by the following formula (5) Wherein the polyimide precursor is a polyimide precursor.

R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each independently represent a hydrogen atom or a Or a monovalent organic group having 20 carbon atoms, which may be the same or different. 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, Lt; / RTI &gt; Formula (I) and in formula (2), R ₁₆ denotes a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or formula (4), R ₁₇ is 1,3-bis ( 4-aminophenoxy) alkane, 1,4-bis (4-aminophenoxy) alkane, Benzene, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzamide, 3,4'-diaminobenzamide, 3,3'-dimethyl-4,4'- Phenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl, 3,7-diamino-dimethyl Dibenzothiophene-5,5-dioxide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-bis (4-aminophenyl) sulfide, - diaminobenzanilide, 1,3- Bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9-bis (4-aminophenyl) fluorene, (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3- Bis (3-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'- Aminophenyl-4-aminobenzoate, bis (4-aminophenoxyphenyl) propane, trimethylene-bis 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, Dihydroxy-4,4'-diaminobiphenyl, 1,3-bis (4-amino From one or more diamines selected from the group consisting of benzene noksi) it represents a moiety other than the terminal two amino groups. 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 a divalent organic group having 1 to 20 carbon atoms. and a represents an integer of 1 or more and 20 or less. The polyimide precursor according to claim 1, wherein the diamine represented by the formula (5) is a diamine represented by the following formula (5-1).

[In the formula (5-1), R ₁₈ is C ₂ H ₄ or C ₄ H _8, and, m, n, p are each independently an integer of not less than 0 40, 12≤ (m + n + p) ≤ 40.] The polyimide precursor according to claim 1, which is represented by the following formula (6).

Wherein R ₁ , R ₂ , R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms And may be the same or different. 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 or more and 100 or less. R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the above formula (3) or (4), R ₁₇ represents a 1,3-bis (4-aminophenoxy) , 4-aminophenoxy) alkane, 1,5-bis (4-aminophenoxy) alkane, 1,4-diaminobenzene, 1,3-diaminobenzene, , 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- Diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,7-diamino-dimethyldibenzothiophene-5,5- (4-aminophenyl) sulfide, 4,4'-diaminobenzanilide, 1,3, 4'-diaminobenzophenone, 3,3'-diaminobenzophenone, - bis (4-aminophenoxy ) -2,2-dimethylpropane, 1,2-bis [2- (4-aminophenoxy) ethoxy] ethane, 9,9- Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, (4-aminophenoxy) biphenyl, 4,4'-bis (3-aminophenoxy) biphenyl, 2,2-bis Aminophenyl-4-aminobenzoate, bis [4- (4-aminobenzoate), 4-aminophenyl- Phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Aminomethyl-3,5,5-trimethylcyclohexane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 3,3'-dihydroxy- , 4'-diaminobiphenyl, 1,3-bis (4-aminophenoxybenzene) From at least one diamine selected from the group eojineun represents a moiety other than the terminal two amino groups. X represents a single bond, a carbonyl group or a sulfonyl group, Y represents a divalent organic group containing an aromatic ring or an aliphatic divalent organic group having 1 to 20 carbon atoms. and a represents an integer of 1 or more and 20 or less. A, B, and C represent mole% of each unit, and satisfy 0 <A <100, 0 <B <100, 0 <C <100, and 0.05 C / (A + B + C) The polyimide precursor according to claim 1 or 3, which is represented by the following formula (6-1).

In the formula (6-1), R ₁₆ represents a tetravalent organic group derived from the tetracarboxylic dianhydride represented by the formula (3) or the formula (4), and R ₁₇ represents a tetravalent organic group having 1 to 90 carbon atoms It represents a divalent organic group, R ₁₈ is C ₂ H ₄ or C ₄ H _8, and, m, n, p are each independently an integer of not less than 0 40 12≤ (m + n + p) ≤40.] (A) a photosensitive resin composition comprising the polyimide precursor according to any one of claims 1 to 3 and (B) a photosensitive agent. The photosensitive resin composition according to claim 5, wherein (B) the photosensitive agent comprises a (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds, and (C) a photopolymerization initiator. The photosensitive resin composition according to claim 6, wherein the (meth) acrylate compound having two or more photopolymerizable unsaturated double bonds together includes a compound having two double bonds and a compound having three or more double bonds Resin composition. The photosensitive resin composition according to claim 5, wherein (B) the photosensitizer comprises a quinone diazide compound. The photosensitive resin composition according to claim 5, which comprises (D) a reactive compound having reactivity with at least one resin selected from the group consisting of a thermosetting resin and a polyimide precursor. The photosensitive resin composition according to claim 5, which further comprises (D) a reactive compound having reactivity with the polyimide precursor, wherein the reactive compound is represented by the following formula (7).

In the formula (7), R ₁₉ is -Ar-Z-Ar- or -Ar-Z-Ar-Z-Ar-, and Z is O or SO ₂ . And R &lt; ₂₀ &gt; is an alkyl group having from 2 to 10 carbon atoms. The photosensitive resin composition according to claim 5, which comprises a compound (E) having at least one structure selected from the group consisting of a phosphate ester structure and a phosphazene structure. delete A photosensitive film comprising a support film layer and the photosensitive resin composition according to claim 5 formed on the support film. 14. The photosensitive film according to claim 13, having a carrier film on one side. The photosensitive film according to claim 13, further comprising a cover film. A coverlay obtained by imidizing the photosensitive resin composition according to claim 5. A flexible printed wiring board characterized in that the photosensitive resin composition according to claim 5 is imidized. A laminate characterized by comprising the coverlay according to claim 16 and a copper-clad laminate.

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