JP2006169409A - Polyimide precursor and photosensitive resin composition using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide precursor usable as a photosensitive polyimide for a rigid and flexible printed board application and enable to imidize at a temperature not higher than 200°C and a photosensitive resin composition using it. <P>SOLUTION: The polyimide precursor is obtained by reacting a polyimide precursor with a specified amic acid structure with a compound with both of a carbon-carbon double bond and an epoxy group in the molecule and/or a compound with both of a carbon-carbon double bond and an isocyanate group in the molecule. The photosensitive resin composition contains a (meth)acrylic compound with a carbon-carbon double bond and a photoinitiator in addition to the polyimide precursor. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyimide precursor having both an imide structure and an amic acid structure, and a photosensitive resin composition using the same.

  Polyimide is excellent in heat resistance among various organic polymers, and thus is widely used in the fields of space and aviation to electronic communication and OA equipment. Particularly in recent years, electronic devices have been rapidly increasing in functionality, performance, and size, and accordingly, electronic components have been required to be smaller and lighter, and photosensitive polyimide has been used. ing.

  The photosensitive polyimide is an amine-bonded photosensitive polyimide (patent document 1) prepared by mixing a polyamic acid with a compound having a tertiary amine and a (meth) acryloyl group, and an ester bond to the carboxyl group of the polyamic acid. An ester-bonded photosensitive polyimide having a methacryloyl group introduced via a carboxylic acid (Patent Documents 2 and 3), an amine compound having a methacryloyl group, or a photosensitive polyimide having a diisocyanate compound introduced into the carboxyl group portion of a polyamic acid (Patent Document 4) Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8), and photosensitive polyimide (patent document 9) in which a polyamic acid and a (meth) acryl compound are mixed were developed.

However, these photosensitive polyimides can only be obtained by imidization after exposure / development in the state of polyamic acid, so it was necessary to apply a temperature of 250 ° C. or higher to FPC, and some photosensitive polyimides have an acroyl group. There is a problem that the film thickness must be removed by heat and the film thickness is greatly reduced. In addition, since heating at 250 ° C. or higher is required, it is impossible to use photosensitive polyimide for rigid and flexible printed circuit boards because other components are deteriorated.
JP 54-145794 A Japanese Patent Publication No.55-030207 Japanese Patent Publication No.55-041422 JP 54-145794 A JP 59-160140 A Japanese Patent Laid-Open No. 03-170547 Japanese Patent Laid-Open No. 03-186847 JP 61-118424 A JP 11-52569 A

  An object of the present invention is to provide a polyimide precursor that can be imidized at a low temperature of 200 ° C. or lower and can be used as a photosensitive polyimide for rigid and flexible printed circuit boards, and a photosensitive composition using the same.

The present invention provides the following polyimide precursors having both an imide structure and an amic acid structure. The polyimide precursor also provides a material for the photosensitive resin composition. That is, a polyimide precursor having both the imide structure and the amide acid structure,
Polyimide obtained by reacting a compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule and / or a compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule The present invention provides a photosensitive resin composition comprising a precursor composition and a (meth) acrylic compound having an unsaturated carbon-carbon double bond as an essential component, and thereby the above-described problems can be solved.

  This will be specifically described below.

The first of the present invention is
A polyimide precursor having both an imide structure represented by formula (1) and an amic acid structure represented by formula (2);
A polyimide precursor obtained by reacting a compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule and / or a compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule body,

（式中Ｒ¹は４価の有機基を示し、Ｒ²はジアミンからアミノ基を除いた２価の有機基、或いはジイソシアネートからイソシアネート基を除いた２価の有機基を、Ｒ³は式（３）を示し、Ｒ⁴はメチル基、エチル基、フェニル基のいずれかを示し、ｘ＝２〜１０、ｙ＝４〜３０を示す。）

(Wherein R ¹ represents a tetravalent organic group, R ² represents a divalent organic group obtained by removing an amino group from a diamine, or a divalent organic group obtained by removing an isocyanate group from a diisocyanate, and R ³ represents a formula ( 3), R ⁴ represents any one of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10 and y = 4 to 30.)

である。

It is.

  With this configuration, imidization can be performed at a low temperature of 200 ° C. or lower.

Moreover, as shown below, when the carboxylic acid of the polyamic acid derived from the silicone diamine of this structure exists, when it is used as a photosensitive resin, it can be developed with an alkaline solution of a developer.
This polyimide precursor can be used not only for photosensitive resin applications, as long as the above properties are utilized.

The second of the present invention is
The polyimide according to the first aspect of the present invention, wherein in the formula (1), a part of R ² represents a divalent organic group obtained by removing an amino group from a diamine having a hydroxyl group and / or a carboxyl group. precursor,
It is.

The third aspect of the present invention is
The polyimide precursor according to the second aspect of the present invention, wherein in the formula (1), a part of R ² is the formula (4)

（Ｒ⁵は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ₃）₂−，−ＣＨ₂−，−ＳＯ₂−，−Ｏ−，−Ｃ（ＣＦ₃）₂−，−ＣＨ（ＣＨ₃）−，−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−，シクロヘキシルのいずれかを、Ｒ⁶とＲ⁷はＨ，ＣＨ₃−，ＣＨ₃ＣＨ₂−のいずれかを、ｍは０〜３を示す。）
である。

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , m is 0 to 3 is shown.)
It is.

The fourth aspect of the present invention is
In the formula (1), a part of R ² is the formula (5), the polyimide precursor according to the second of the present invention,

（Ｒ⁵は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ₃）₂−，−ＣＨ₂−，−ＳＯ₂−，−Ｏ−，−Ｃ（ＣＦ₃）₂−，−ＣＨ（ＣＨ₃）−，−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−，シクロヘキシルのいずれかを、Ｒ⁶とＲ⁷はＨ，ＣＨ₃−，ＣＨ₃ＣＨ₂−のいずれかを、ｎは１〜５を示す。）
である。

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , n is 1 to 5 is shown.)
It is.

The fifth aspect of the present invention is
In the formula (1), a part of R ² is the formula (6), the polyimide precursor according to the second of the present invention,

（Ｒ⁵は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ₃）₂−，−ＣＨ₂−，−ＳＯ₂−，−Ｏ−，−Ｃ（ＣＦ₃）₂−，−ＣＨ（ＣＨ₃）−，−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−，シクロヘキシルのいずれかを、Ｒ⁶とＲ⁷はＨ，ＣＨ₃−，ＣＨ₃ＣＨ₂−のいずれかを、ｒは０〜５を示す。）
である。

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , r is 0 to 5 is shown.)
It is.

The sixth of the present invention is
(A) In addition to 100 parts by weight of the polyimide precursor according to any one of the first to fifth aspects of the present invention, (B) 1 to 400 parts by weight of a (meth) acrylic compound having an unsaturated carbon-carbon double bond A photosensitive resin composition as an essential component;
It is.

  By being this structure, since it can be imidized at a low temperature of 200 ° C. or lower, it can be used for various applications such as rigid and flexible printed circuit boards.

The seventh of the present invention is
In addition to the photosensitive resin composition according to the sixth aspect of the present invention, (C) the photoreaction initiator is 0.1% relative to 100 parts by weight of the polyimide precursor according to any one of the first to fifth aspects of the present invention. A photosensitive resin composition having 01 to 50 parts by weight as an essential component;
It is.

The eighth of the present invention is
In addition to the photosensitive resin composition according to the seventh aspect of the present invention, with respect to 100 parts by weight of the polyimide precursor according to any one of the first to fifth aspects of the present invention,
(D) 0.01 to 30 parts by weight of a compound having an ethylenically unsaturated carbon-carbon double bond and a tertiary amino group in the molecule or a compound having an ethylenically unsaturated carbon-carbon double bond and an amide group A photosensitive resin composition as an essential component;
It is.

The ninth of the present invention is
The photosensitive resin composition according to any one of the sixth to eighth aspects of the present invention, wherein the polyimide precursor according to any one of the first to fifth aspects of the present invention is dehydrated and cyclized into a polyimide,
It is.

The tenth aspect of the present invention is
A photosensitive dry film resist comprising the photosensitive resin composition according to the ninth aspect of the present invention;
It is.

  The polyimide precursor used in the present invention will be described. The polyimide precursor of the present invention has both an imide structure and an amide acid structure.

That is, the polyimide resin of the present invention is
A polyimide precursor having both an imide structure represented by formula (1) and an amic acid structure represented by formula (2);
It is obtained by reacting a compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule and / or a compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule.

（式中Ｒ¹は４価の有機基を示し、Ｒ²はジアミンからアミノ基を除いた２価の有機基、或いはジイソシアネートからイソシアネート基を除いた２価の有機基を、Ｒ³は式（３）を示し、Ｒ⁴はメチル基、エチル基、フェニル基のいずれかを示し、ｘ＝２〜１０、ｙ＝４〜３０を示す。）

(Wherein R ¹ represents a tetravalent organic group, R ² represents a divalent organic group obtained by removing an amino group from a diamine, or a divalent organic group obtained by removing an isocyanate group from a diisocyanate, and R ³ represents a formula ( 3), R ⁴ represents any one of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10 and y = 4 to 30.)

The manufacturing method of the polyimide precursor of this invention is demonstrated.
First, an acid dianhydride and a diamine compound or an acid dianhydride and a diisocyanate compound are reacted in an organic polar solvent to have an acid dianhydride at both ends and an imide structure in the molecular main chain. The oligomer which has is synthesized. The number of equivalents in this case is acid dianhydride> diamine compound or acid dianhydride> diisocyanate.

  A method for synthesizing an oligomer having an acid dianhydride at both ends obtained by reacting an acid dianhydride and a diamine compound and having an imide structure in the molecular main chain will be described.

  An acid dianhydride and a diamine compound are subjected to an addition polymerization reaction in an organic solvent at a reaction temperature of 80 ° C. or lower, preferably 50 ° C. or lower for 1 to 12 hours, to form a polyamic acid (raw material of an acid dianhydride-terminated oligomer) Having an amic acid structure in the molecular main chain). The number of equivalents in this case is acid dianhydride> diamine compound, and the ratio of acid dianhydride ÷ diamine compound is more than 1 and 10 or less, preferably 1.1 or more and 5 or less, more preferably 1.3 or more and 3 or less.

  As an organic solvent in this polymerization reaction, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2- Examples include pyrrolidone and hexamethylenephosphoamide, and these can be used alone or in combination of two or more.

  The polyamic acid which is the raw material of the acid dianhydride terminal oligomer obtained as described above is then dehydrated and cyclized to form an acid dianhydride terminal oligomer (having an imide structure in the molecular main chain and both terminals). Have an acid anhydride structure). A known method can be used as a method for producing a polyimide by dehydrating cyclization of polyamic acid. For example, a thermal cyclization method by refluxing with toluene, xylene or the like, or a chemical cyclization method with an aromatic tertiary amine such as acetic anhydride and pyridine can be used.

  As another method for producing a polyimide by dehydrating cyclization of polyamic acid, there is a method of heating and dehydrating a polyamic acid solution under reduced pressure. In this method, water generated by imidization is heated and decompressed and actively removed from the system, so that hydrolysis can be suppressed. Moreover, the polymerization reaction of the polyamic acid was stopped by mixing the raw acid dianhydride with a tetracarboxylic acid which was ring-opened by hydrolysis or one of the acid dianhydride hydrolyzed. Even in the case, it can be expected that the ring-opened acid anhydride is closed again by heating under reduced pressure during imidization.

  Any acid dianhydride can be used for the acid anhydride of the present invention.

  Although it will not specifically limit if it is an acid dianhydride, For example, the following alicyclic tetracarboxylic anhydride or aromatic tetracarboxylic dianhydride is mentioned.

  2,2′-hexafluoropropylidenediphthalic dianhydride, 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, butanetetra Carboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbonane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetra Carboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2 - oct-7-ene-2,3,5,6-tetracarboxylic acid aliphatic, such as anhydrides or alicyclic tetracarboxylic dianhydride.

  Pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bi (3,4-Dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid Dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenyl) Aromatic tetracarboxylic dianhydrides such as phthalic acid) -4,4′-diphenyl ether dianhydride and bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride.

  These alicyclic tetracarboxylic anhydrides or aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more.

  In order to obtain a polyimide having high solubility in an organic solvent, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 2,2′-hexafluoropropylidenediphthalic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 4,4- (4,4′-isopropylidenediphenoxy) bisphthalic anhydride, 2,2-bis (4-hydroxyphenyl) propane Dibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetra It is desirable to partially use phenylsilane tetracarboxylic dianhydride and 1,2-ethanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride.

  Any diamine compound having two amino groups can be used for the diamine of the present invention.

Although it will not specifically limit if it is a diamine compound, For example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminophenylethane, 4,4'-diaminophenyl ether, 4, 4'-didiaminophenyl sulfide, 4,4'-didiaminophenyl sulfone, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4'-diaminobiphenyl, 5-amino-1- (4'-amino Phenyl) -1,3,3-trimethylindane, 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 4,4′-diaminobenzanilide, 3,5-diamino- 3'-trifluoromethylbenzanilide, 3,5-diamino-4'-trifluoromethylbenzanilide, 3,4'-diaminodiphe Ether, 2,7-diaminofluorene, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4'-methylene-bis (2-chloroaniline), 2,2 ', 5,5'-tetra Chloro-4,4′-diaminobiphenyl, 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 '-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) -biphenyl, 1,3'-bis (4-aminophenoxy) benze 9,9-bis (4-aminophenyl) fluorene, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2′-bis [4 Aromatic diamines such as-(4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4'-bis [4- (4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl An aromatic diamine having two amino groups bonded to an aromatic ring such as diaminotetraphenylthiophene and a hetero atom other than the nitrogen atom of the amino group; 1,1-metaxylylenediamine, 1,3-propanediamine , Tetramethylenediamine, pentamethylenediamine, octamethylenediamine, nonamethylenediamine, 4, - diamino heptamethylene diamine, 1,4-diaminocyclohexane, isophorone diamine, tetrahydrodicyclopentadiene cyclopentadienylide diamine, hexahydro-4,7-meth Noin mite range diamine, tricyclo [6,2,1,0 ^2.7] -Undecylenedimethyl diamine, aliphatic diamines such as 4,4'-methylenebis (cyclohexylamine) and alicyclic diamines, 4,6-diaminoresorcinol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4, Such as 4′-diamino-3,3′-dihydroxybiphenyl, 4,4′-diamino-2,2′-dihydroxybiphenyl, 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl, etc. Hydroxybiphenyl compounds, 3,3′-diamino-4,4′-dihydroxydi Phenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis [3-amino-4-hydroxy Phenyl] hexafluoropropane, hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane, 3,3′-diamino-4,4′-dihydroxy Diphenyl ether, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 4,4′-diamino-2,2′-dihydroxydiphenyl ether, 4,4′-diamino-2,2 ′, 5,5′-tetra Hydroxydiphenyl ether compounds such as hydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydride Xidiphenyl sulfone, 4,4′-diamino-3,3′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2′-dihydroxydiphenyl sulfone, 4,4′-diamino-2,2 ′, 5 Diphenyl sulfone compounds such as 5′-tetrahydroxydiphenyl sulfone, bis [(hydroxyphenyl) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 2, Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as 2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone, diaminophenols such as 2,4-diaminophenol, 3,3′-diamino -4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihai Bis (hydroxyphenoxy) biphenyl compounds such as roxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 4 , 4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino-4-hydroxyphenyl] propane, 4, Bis (hydroxyphenoxy) biphenyl compounds such as 4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, diaminophthalic acids such as 2,5-diaminoterephthalic acid, 3,3′-diamino-4 , 4′-dicarboxybiphenyl, 4,4′-diamino-3,3′-dicarboxybiphenyl, 4,4′-diamino-2,2 ′ -Carboxybiphenyl compounds such as dicarboxybiphenyl, 4,4'-diamino-2,2 ', 5,5'-tetracarboxybiphenyl, 3,3'-diamino-4,4'-dicarboxydiphenylmethane, 2, 2-bis [3-amino-4-carboxyphenyl] propane, 2,2-bis [4-amino-3-carboxyphenyl] propane, 2,2-bis [3-amino-4-carboxyphenyl] hexafluoropropane Carboxydiphenylalkanes such as 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenylmethane, 3,3′-diamino-4,4′-dicarboxydiphenyl ether, 4,4′-diamino -3,3'-dicarboxydiphenyl ether, 4,4'-diamino-2,2'-dicarboxydiphenyl ether, 4,4'-di Carboxydiphenyl ether compounds such as mino-2,2 ′, 5,5′-tetracarboxydiphenyl ether, 3,3′-diamino-4,4′-dicarboxydiphenyl sulfone, 4,4′-diamino-3,3′- Diphenyl sulfone compounds such as dicarboxydiphenyl sulfone, 4,4′-diamino-2,2′-dicarboxydiphenyl sulfone, 4,4′-diamino-2,2 ′, 5,5′-tetracarboxydiphenyl sulfone, 2 Bis [(carboxyphenoxy) phenyl] alkane compounds such as 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxy) Bis [(carboxyphenoxy) phenyl] sulfone compounds such as phenoxy) phenyl] sulfone, 3 And diaminobenzoic acid such as 5-diaminobenzoic acid. These diamine compounds can be used alone or in combination of two or more. Among these diamines, it is particularly preferable to use a part of the compounds represented by formula (4), formula (5), and formula (6), more preferably 5% mol or more in the diamine component other than silicone diamine, It is preferable to use 10 mol% or more.

（Ｒ⁵は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ₃）₂−，−ＣＨ₂−，−ＳＯ₂−，−Ｏ−，−Ｃ（ＣＦ₃）₂−，−ＣＨ（ＣＨ₃）−，−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−，シクロヘキシルのいずれかを、Ｒ⁶とＲ⁷はＨ，ＣＨ₃−，ＣＨ₃ＣＨ₂−のいずれかを、ｍは０〜３を示す。）

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , m is 0 to 3 is shown.)

（Ｒ⁵は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ₃）₂−，−ＣＨ₂−，−ＳＯ₂−，−Ｏ−，−Ｃ（ＣＦ₃）₂−，−ＣＨ（ＣＨ₃）−，−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−，シクロヘキシルのいずれかを、Ｒ⁶とＲ⁷はＨ，ＣＨ₃−，ＣＨ₃ＣＨ₂−のいずれかを、ｎは１〜５を示す。）

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , n is 1 to 5 is shown.)

式（６）
（Ｒ⁵は−，−（Ｃ＝Ｏ）−，−Ｃ（ＣＨ₃）₂−，−ＣＨ₂−，−ＳＯ₂−，−Ｏ−，−Ｃ（ＣＦ₃）₂−，−ＣＨ（ＣＨ₃）−，−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−，シクロヘキシルのいずれかを、Ｒ⁶とＲ⁷はＨ，ＣＨ₃−，ＣＨ₃ＣＨ₂−のいずれかを、ｒは０〜５を示す。）
次に酸二無水物とジイソシアネート化合物とを反応させて得られる、酸二無水物を両末端に有し、かつ、分子主鎖中にイミド構造を有するオリゴマー、の合成法について説明する。

Formula (6)
(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , r is 0 to 5 is shown.)
Next, a method for synthesizing an oligomer having an acid dianhydride at both ends and having an imide structure in the molecular main chain obtained by reacting an acid dianhydride and a diisocyanate compound will be described.

  An acid dianhydride and a diisocyanate compound are subjected to a polycondensation reaction in an organic solvent for 1 to 12 hours to decarboxylate to obtain an acid dianhydride terminal oligomer (having an imide structure in the molecular main chain). The number of equivalents in this case is acid dianhydride> diisocyanate compound, and the ratio of acid dianhydride ÷ diisocyanate compound is more than 1 and 10 or less, preferably 1.1 or more and 5 or less, more preferably 1.3 or more and 3 or less.

  The conditions for the polycondensation reaction of acid dianhydride and diisocyanate compound in an organic solvent include, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, After heating at room temperature to 80 ° C in a polar solvent such as N, N-diethylacetamide, N-methyl-2-pyrrolidone or hexamethylenephosphoamide, the reaction is further heated to about 150 to 200 ° C to promote the reaction. At this time, it is more preferable to reduce the pressure because the decarboxylation reaction is promoted.

  The acid dianhydride used in the polyimide precursor of the present invention is the same acid dianhydride as that used in the synthesis of the acid dianhydride terminal oligomer obtained by reacting the acid dianhydride and the diamine compound. Can be used.

  Although the diisocyanate used for the polyimide precursor of this invention will not be specifically limited if it is a diisocyanate, The following diisocyanate can be illustrated.

  For example, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6- Hexamethylene diisocyanate, lysine diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate), 1,3-bis (isocyanate) -Tomethyl) -cyclohexane, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, Rubodiimidized diphenylmethane polyisocyanate, tolidine diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate Neat, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate and the like can be raised.

The oligomer (having an imide structure in the molecular main chain) having the acid dianhydride thus obtained at both ends and the silicone diamine represented by the formula (7) in an organic solvent is preferably 100 ° C. or lower, preferably Can synthesize the polyimide precursor of the present invention by addition polymerization reaction at a reaction temperature of 50 ° C. or lower for 0.5 to 12 hours. (In the formula, R ⁴ represents one of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10 and y = 4 to 30).

本発明のポリイミド前駆体は、０．５ｇ／Ｎ−メチル−２−ピロリドン１００ｍｌの濃度溶液として、３０℃における対数粘度が０．２〜４．０の範囲であり、より好ましくは０．３〜２．０の範囲である。

The polyimide precursor of the present invention has a logarithmic viscosity at 30 ° C. in the range of 0.2 to 4.0, more preferably 0.3 to 0.5 g / N-methyl-2-pyrrolidone as a 100 ml concentration solution. The range is 2.0.

  As an organic solvent in this polymerization reaction, for example, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2- Pyrrolidone, hexamethylenephosphoamide, dioxolane, tetrahydrofuran, dioxolane and the like can be mentioned, and these can be used alone or in admixture of two or more.

  Usually, when a polyamic acid derived from an aromatic diamine is closed and imidized, the molecular chain length is shortened as shown in Scheme (1). Therefore, in order to imidize, it is necessary to heat at a temperature higher than the temperature at which the entire molecular chain can move, and it is necessary to raise the temperature to 250 ° C or higher.

それに反して、シリコーンジアミン由来のポリアミド酸は、シロキサン部位が低温で自由に振動できるため、分子鎖全体が運動できる温度以下の温度でも、イミド化することができる（イミド化のスキームを、スキーム（２）で表す）。よって、本発明のポリイミド前駆体は、シリコーンジアミン由来のポリアミド酸構造以外のポリアミド酸部位を既にイミド化しているため、２００℃以下の低温でイミド化を行うことが出来るのである。また、シリコーンジアミン由来のポリアミド酸のカルボン酸の影響で、感光性樹脂として用いた際には、現像液のアルカリ性溶液により現像可能となる。

On the other hand, since the polyamic acid derived from silicone diamine can freely vibrate at a low temperature at the siloxane site, it can be imidized even at a temperature below the temperature at which the entire molecular chain can move (the imidization scheme is represented by scheme ( 2)). Therefore, since the polyimide precursor of this invention has already imidated the polyamic-acid site | parts other than the polyamic acid structure derived from a silicone diamine, it can imidize at the low temperature of 200 degrees C or less. Further, due to the influence of the carboxylic acid of the polyamic acid derived from silicone diamine, it can be developed with an alkaline solution of a developer when used as a photosensitive resin.

  In other words, the polyimide precursor of the present invention is a polyamic acid derived from silicone diamine (having an amide structure) and all other polyamic acids derived from diamine are imidized (having an imide structure).

本発明の式（１）と式（２）の構成モル比は、式（１）／式（２）＝０．１〜５０の範囲内であり、好ましくは式（１）／式（２）＝０．２〜３０、更に好ましくは式（１）／式（２）＝０．３〜１０である。この範囲を逸脱すると、良好な感光能が得られなかったり、耐熱性が損なわれる傾向にあり好ましくない。

The constituent molar ratio of the formulas (1) and (2) of the present invention is within the range of formula (1) / formula (2) = 0.1-50, preferably formula (1) / formula (2). = 0.2 to 30, more preferably formula (1) / formula (2) = 0.3 to 10. Deviating from this range is not preferable because good photosensitivity cannot be obtained and heat resistance tends to be impaired.

A polyimide precursor having an imide structure represented by the formula (1) and an amic acid structure represented by the formula (2) thus obtained,
A compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule and / or a compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule are reacted.

First of all,
A compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule;
The reaction with a polyimide precursor having both an imide structure represented by the formula (1) and an amic acid structure represented by the formula (2) will be described.

A part of the carboxyl group of the polyimide precursor having an imide structure represented by the formula (1) and an amic acid structure represented by the formula (2);
By reacting a compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule, a double bond can be easily introduced into the side chain.

The compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule is not particularly limited as long as it has an epoxy group and an unsaturated carbon-carbon double bond in the molecule. It can be illustrated. That is, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, formula (8), formula (9), and the like. (However, R < ⁸ >, R < ⁹ > shows hydrogen or a methyl group.) These can be used individually or in mixture of 2 or more types.

  Even when a compound having an epoxy group and an unsaturated carbon-carbon triple bond is used instead of a compound having both a carbon double bond and an epoxy group in the molecule, the effect when used as a photosensitive resin is the same, preferably Can be used. The compound having an epoxy group and an unsaturated carbon-carbon triple bond is not particularly limited as long as it has an epoxy group and an unsaturated carbon-carbon triple bond in the molecule, and can be exemplified as follows. That is, propargyl glycidyl ether, glycidyl propiolate, ethynyl glycidyl ether and the like. These may be used alone or in combination of two or more.

  The solvent used for the reaction is not particularly reactive with an epoxy group, and can be used as long as it dissolves a polyimide precursor having both an imide structure represented by the formula (1) and an amide acid structure represented by the formula (2). It is not limited. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide Pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, ether solvents such as tetrahydrofuran, dioxane and dioxolane, alcohol solvents such as methanol, ethanol and butanol, cellosolve such as butyl cellosolve, or Hexamethylphosphoramide, γ-butyrolactone, etc., and aromatic hydrocarbons such as xylene and toluene can also be used. These can be used alone or as a mixture. In most cases, the epoxy-modified polyimide of the present invention is finally used after the solvent is removed. Therefore, it is important to select one having a boiling point as low as possible.

  In order to react a compound having both of these unsaturated carbon-carbon double bond and epoxy group in the molecule with the polyimide precursor having the structure of the formula (1) and the structure of the formula (2), these are used. It is dissolved in an organic solvent and reacted by heating. Although any dissolution method may be used, the reaction temperature is preferably 40 ° C. or higher and 130 ° C. or lower. Especially for an epoxy compound having an unsaturated carbon-carbon double bond or an unsaturated carbon-carbon triple bond, the temperature is such that the unsaturated carbon-carbon double bond and the unsaturated carbon-carbon triple bond are not decomposed or crosslinked by heat. The reaction is preferably performed at a temperature of 40 ° C. to 100 ° C., more preferably 50 ° C. to 90 ° C. The reaction time is about several minutes to about 8 hours.

next,
A compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule;
The reaction with a polyimide precursor having both an imide structure represented by the formula (1) and an amic acid structure represented by the formula (2) will be described.

A compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule will be described. Although it will not specifically limit if it has an isocyanate group and an unsaturated carbon-carbon double bond double bond in a molecule | numerator, The following compounds can be illustrated.
Examples of the compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule include methacryloyl isocyanate, acryloyl isocyanate, methacryloylethyl isocyanate, acryloylethyl isocyanate, Methacryloxyethyl isocyanate, acryloxyethyl isocyanate, vinyl dimethylbenzyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-methacryloyloxyethyl isocyanate, etc. Can be mentioned. These may be used alone or in combination of two or more.

  A polyimide precursor having both the imide structure represented by the above formula (1) and the amic acid structure represented by the formula (2), and a compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule; Examples of the solvent used in the reaction include the following. That is, N, N-dimethylformamide, N, N-diethylformamide, N-methylformanilide, N-formylpiperidine, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N N-substituted amides such as methyl-α-pyrrolidone, N-methyl-α-piperidone, N-methylcaprolactam, N-tetramethylurea, N-acetyl-α-pyrrolidone, N-acetyl-α-piperidone, N- N-substituted ureas such as acetylcaprolactam, N-substituted thioureas such as N-tetramethylthiourea, dimethyl sulfoxide, tetramethylene sulfoxide, diethyl sulfoxide, diisopropyl sulfoxide, di-n-propyl sulfoxide, diisobutyl sulfoxide, di-n-butyl Suruhokisodo such as sulfoxide, and hexamethyl phosphoryl amide, N-substituted Hosuhoriruamido such as hexaethyl phosphoryl amide, benzene, toluene, xylene, ether, tetrahydrofuran, organic solvent such as dioxane. These can be used alone or as a mixture. The (meth) acrylic compound having an unsaturated carbon-carbon double bond that is the component (B) used in the present invention will be described.

  In addition to the polyimide composition of the present invention, (B) a (meth) acrylic compound having an unsaturated carbon-carbon double bond is added to obtain a photosensitive resin composition. The (meth) acrylic compound having an unsaturated carbon-carbon double bond used in the present invention is a methacrylic compound having an unsaturated carbon-carbon double bond and / or an acrylic compound having an unsaturated carbon-carbon double bond. That is. Although it does not specifically limit as long as it is a (meth) acryl compound which has an unsaturated carbon-carbon double bond, The following can be illustrated.

  For example, bisphenol F EO (ethylene oxide) modified (n = 2-50) diacrylate, bisphenol A EO modified (n = 2-50) diacrylate, bisphenol S EO modified (n = 2-50) diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolpropane tetraacrylate, tetraethylene glycol di Acrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethylene glycol dimethacrylate , Pentaerythritol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexamethacrylate, tetramethylolpropane tetramethacrylate, tetraethylene glycol dimethacrylate, methoxydiethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, β-methacryloyloxy Ethyl hydrogen phthalate, β-methacryloyloxyethyl hydrogen succinate, 3-chloro-2-hydroxypropyl methacrylate, stearyl methacrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, β-acryloyl Oxyethyl hydrogen succinate, lauryl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl Glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy 1,3 dimethacryloxypropane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxy diethoxy) Phenyl] propane, 2,2-bis [4- (methacryloxy polyethoxy) phenyl] propane, polyethylene glycol diacrylate, triplicate Lopylene glycol diacrylate, polypropylene glycol diacrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [4- (acryloxypolyethoxy) phenyl] propane, 2-hydroxy 1-acryloxy 3-methacryloxypropane, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, nonylphenoxypolyethylene glycol acrylate, nonylphenoxypolypropylene glycol acrylate, 1- Acryloyloxypropyl-2-phthalate, isostearyl acrylate, polio Siethylene alkyl ether acrylate, nonylphenoxyethylene glycol acrylate, polypropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-mexanediol dimethacrylate, 1,9-nonanediol methacrylate, 2,4-diethyl-1,5-pentanediol dimethacrylate, 1,4-cyclohexanedimethanol dimethacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 2,2 Hydrogenated bis [4- (acryloxy polyethoxy) phenyl] propane, 2,2-bis [4- (acryloxy polypropoxy) phenyl] propane, 2,4-diethyl-1,5- Nthanediol diacrylate, ethoxylated totimethylolpropane triacrylate, propoxylated tomethylolpropane triacrylate, isocyanuric acid tri (ethane acrylate), pentathritol tetraacrylate, ethoxylated pentathritol tetraacrylate, propoxylated pentathritol tetraacrylate Ditrimethylolpropane tetreacrylate, dipentaerythritol polyacrylate, triallyl isocyanurate, glycidyl methacrylate, glycidyl allyl ether, 1,3,5-triacryloylhexahydro-s-triazine, triallyl 1,3,5-benzenecarboxylate, Triallylamine, triallyl citrate, triallyl phosphate, allobarbital, diallylamine , Diallyldimethylsilane, diallyl disulfide, diallyl ether, zalyl sialate, diallyl isophthalate, diallyl terephthalate, 1,3-dialyloxy-2-propanol, diallyl sulfide diallyl maleate, 4,4'-isopropylidene diphenol dimethacrylate 4,4′-isopropylidenediphenol diacrylate and the like. In order to improve the crosslink density, it is particularly desirable to use a bifunctional or higher monomer.

  Other compounds having an unsaturated carbon-carbon double bond include styrene, divinylbenzene, vinyl-4-t-butylbenzoate, vinyl n-butyl ether, vinyl isobutyl ether, vinyl n-butyrate, vinyl-n-caprolate, vinyl Examples include vinyl compounds such as n-caprylate, and allyl compounds such as triallyl isocyanurate and diallyl phthalate.

  The amount of the other compound having an unsaturated carbon-carbon double bond is not particularly limited as long as it does not impair the photosensitivity and flame retardancy.

  The compound having an unsaturated carbon-carbon double bond is preferably blended in an amount of 1 to 400 parts by weight, more preferably 3 to 300 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. If it deviates from the range of 1 to 400 parts by weight, the intended effect may not be obtained. In addition, as a compound having an unsaturated carbon-carbon double bond, one type of compound may be used. You may mix and use seeds. Moreover, you may mix radical generators, such as a peroxide.

The photoreaction initiator that is the component (C) used in the present invention will be described.
The photoinitiator of this invention is a general term for the compound which generate | occur | produces a radical by light irradiation. Although it will not specifically limit if a radical is generate | occur | produced by light irradiation of 250-450 nm, The following can be illustrated.

  For example, acylphosphine oxide compounds represented by the following formulas (10) and (11) are mentioned. The radical generated thereby reacts with a reactive group having two bonds (vinyl, acryloyl, methacryloyl, allyl, etc.) to promote crosslinking.

（式中、Ｒ¹⁰，Ｒ¹¹，Ｒ¹²，Ｒ¹³，Ｒ¹⁴びＲ¹⁵、Ｃ₆Ｈ₅−，Ｃ₆Ｈ₄（ＣＨ₃）−，Ｃ₆Ｈ₂（ＣＨ₃）₃−，（ＣＨ₃）₃Ｃ−，Ｃ₆Ｈ₃Ｃｌ₂−，メトキシ基，エトキシ基を表す。）

(Wherein R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ^{14 and} R ¹⁵ , C ₆ H _5- , C ₆ H ₄ (CH ₃ )-, C ₆ H ₂ (CH ₃ ) _3- , ( CH ₃ ) ₃ C—, C ₆ H ₃ Cl ₂ —, a methoxy group, an ethoxy group.

In particular, the acylphosphine oxide represented by the formula (11) is preferable because four radicals are generated by α-cleavage. (Formula (10) generates two radicals)
Various peroxides can be used in combination with the following sensitizers as radical initiators. In particular, a combination of 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone and a sensitizer is particularly preferable. In order to achieve the photosensitivity of the photosensitive resin composition used in the present invention, an increase is required. Sensitizers can be included. Preferred examples of the sensitizer include mihiraketone, bis-4,4′-diethylaminobenzophenone, benzophenone, camphorquinone, benzyl, 4,4′-dimethylaminobenzyl, 3,5-bis (diethylaminobenzylidene) -N-methyl. -4-piperidone, 3,5-bis (dimethylaminobenzylidene) -N-methyl-4-piperidone, 3,5-bis (diethylaminobenzylidene) -N-ethyl-4-piperidone, 3,3′-carbonylbis ( 7-diethylamino) coumarin, riboflavin tetrabutyrate, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 3,5-dimethyl Oxanthone, 3,5-diisopropylthioxanthone, 1-phenyl-2- (ethoxycarbonyl) oxyiminopropan-1-one, benzoin ether, benzoin isopropyl ether, benzanthrone, 5-nitroacenaphthene, 2-nitrofluorene, anthrone, 1,2-benzanthraquinone, 1-phenyl-5-mercapto-1H-tetrazole, thioxanthen-9-one, 10-thioxanthenone, 3-acetylindole, 2,6-di (p-dimethylaminobenzal) -4 -Carboxycyclohexanone, 2,6-di (p-dimethylaminobenzal) -4-hydroxycyclohexanone, 2,6-di (p-diethylaminobenzal) -4-carboxycyclohexanone, 2,6-di (p-diethylamino) Benza ) -4-hydroxycyclohexanone, 4,6-dimethyl-7-ethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 7-diethylamino-3- (1-methylbenzimidazolyl) coumarin, 3- (2-benzimidazolyl)- 7-diethylaminocoumarin, 3- (2-benzothiazolyl) -7-diethylaminocoumarin, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) Examples include, but are not limited to, quinoline, 2- (p-dimethylaminostyryl) zenzothiazole, 2- (p-dimethylaminostyryl) -3,3-dimethyl-3H-indole.

  The sensitizer is preferably blended in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. If the amount is outside the range of 0.01 to 50 parts by weight, the sensitization effect may not be obtained or the developability may be adversely affected. In addition, as a sensitizer, one type of compound may be used and several types may be mixed and used.

  In addition, the photosensitive resin composition used in the present invention can contain a photopolymerization auxiliary agent in order to achieve practical photosensitivity. Examples of the photopolymerization assistant include 4-diethylaminoethylbenzoate, 4-dimethylaminoethylbenzoate, 4-diethylaminopropylbenzoate, 4-dimethylaminopropylbenzoate, 4-dimethylaminoisoamylbenzoate, N-phenylglycine, N- Methyl-N-phenylglycine, N- (4-cyanophenyl) glycine, 4-dimethylaminobenzonitrile, ethylene glycol dithioglycolate, ethylene glycol di (3-mercaptopropionate), trimethylolpropane thioglycolate, Trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra (3-mercaptopropionate), trimethylol eta Trithioglycolate, trimethylolpropane trithioglycolate, trimethylolethanetri (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), thioglycolic acid, α-mercaptopropionic acid, t -Butylperoxybenzoate, t-butylperoxymethoxybenzoate, t-butylperoxynitrobenzoate, t-butylperoxyethylbenzoate, phenylisopropylperoxybenzoate, di-t-butyldiperoxyisophthalate, tri-t-butyltriperoxytrimethyl Tate, tri-t-butyltriperoxytrimesitate, tetra-t-butyltetraperoxypyromellitate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexa 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3,4,4′-tetra (t-amylperoxycarbonyl) benzophenone, 3,3 ′, 4,4 ′ -Tetra (t-hexylperoxycarbonyl) benzophenone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (p-azidobenzal) -4-carboxycyclohexanone, 2,6-di (p -Azidobenzal) -4-methoxycyclohexanone, 2,6-di (p-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (p-azidobenzal) -1-methyl-4-piperidone, 3,5-di (P-azidobenzal) -4-piperidone, 3,5-di (p-azibenzal) -N-acetyl-4-pipe Don, 3,5-di (p-azidobenzal) -N-methoxycarbonyl-4-piperidone, 2,6-di (p-azidobenzal) -4-hydroxycyclohexanone, 2,6-di (m-azidobenzal) -4 -Carboxycyclohexanone, 2,6-di (m-azidobenzal) -4-methoxycyclohexanone, 2,6-di (m-azidobenzal) -4-hydroxymethylcyclohexanone, 3,5-di (m-azidobenzal)- N-methyl-4-piperidone, 3,5-di (m-azidobenzal) -4-piperidone, 3,5-di (m-azidobenzal) -N-acetyl-4-piperidone, 3,5-di (m-azidobenzal) ) -N-methoxycarbonyl-4-piperidone, 2,6-di (p-azidocinnamylidene) -4-hydroxycyclohexa 2,6-di (p-azidocinnamylidene) -4-carboxycyclohexanone, 2,6-di (p-azidocinnamylidene) -4-cyclohexanone, 3,5-di (p-azidocinnamylidene) Den) -N-methyl-4-piperidone, 4,4′-diazidochalcone, 3,3′-diazidochalcone, 3,4′-diazidochalcone, 4,3′-diazidochalcone, 1,3 -Diphenyl-1,2,3-propanetrione-2- (o-acetyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (on-propylcarbonyl) oxime, 1, 3-diphenyl-1,2,3-propanetrione-2- (o-methoxycarbonyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-ethoxycarbonyl) oxy Shim, 1,3-diphenyl-1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3-diphenyl-1,2,3-propanetrione-2- (o-phenyloxycarbonyl) Oxime, 1,3-bis (p-methylphenyl) -1,2,3-propanetrione-2- (o-benzoyl) oxime, 1,3-bis (p-methoxyphenyl) -1,2,3- Propanetrione-2- (o-ethoxycarbonyl) oxime, 1- (p-methoxyphenyl) -3- (p-nitrophenyl) -1,2,3-propanetrione-2- (o-phenyloxycarbonyl) oxime However, it is not limited to these. Further, as another auxiliary agent, trialkylamines such as triethylamine, tributylamine, and triethanolamine can be mixed.

  The photopolymerization assistant is preferably blended in an amount of 0.01 to 50 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyimide precursor of the present invention. If the content falls outside the range of 0.01 to 50 parts by weight, the intended sensitization effect may not be obtained, or the developability may be adversely affected. In addition, one type of compound may be used as a photopolymerization assistant, and several types may be mixed.

  A compound having an ethylenically unsaturated carbon-carbon double bond and a tertiary amino group and a compound having an ethylenically unsaturated carbon-carbon double bond and an amide group, which are components (D) used in the present invention, will be described.

  This compound will not be specifically limited if it is a compound which has an ethylenically unsaturated carbon-carbon double bond and a tertiary amino group in a molecule | numerator, or has an ethylenically unsaturated carbon-carbon double bond and an amide group.

  Preferable specific examples of the compound having an ethylenically unsaturated carbon-carbon double bond and a tertiary amino group include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, N, N-dimethylaminoethyl. Methacrylamide, N, N-dimethylaminopropyl methacrylamide, N, N-diethylaminoethyl methacrylamide, N, N-diethylaminopropyl methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, N, N-dimethylaminoethyl acrylamide, N, N-dimethylaminopropyl acrylamide, N, N-diethylaminoethyl acrylamide, N, N-diethylaminopropyl acrylamide, etc. Including but not limited to.

  Preferred specific examples of the compound having an ethylenically unsaturated carbon-carbon double bond and an amide group include acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-ethyl methacrylamide, and N-ethyl acrylamide. N-isopropylmethacrylamide, N-isopropylacrylamide, N-butylmethacrylamide, N-butylacrylamide, diacetoneacrylamide, diacetonemethacrylamide, N-cyclohexylmethacrylamide, N-cyclohexylacrylamide, N-methylolacrylamide, Acryloylmorpholine, methacryloylmorpholine, acryloylpiperidine, methacryloylpiperidine, crotonamide, N-methylcrotonamide, N-isopropylc Ton'amido, N- butyl crotonamide, acetic arylamide, but such allyl amide propionic acid without limitation. In particular, aminoacrylate derivatives and acrylamide derivatives are preferred in terms of sensitivity.

  The photosensitive resin composition of the present invention may contain an epoxy compound in addition to the polyimide precursor, the (meth) acryl compound, and the photoinitiator.

  The epoxy compound is not particularly limited as long as it has an epoxy group in the molecule, and can be exemplified as follows.

  For example, bisphenol resin such as Epicoat 828 (manufactured by Yuka Shell), orthocresol novolak resin such as 180S65 (manufactured by Yuka Shell), bisphenol A novolak resin such as 157S70 (manufactured by Yuka Shell), 1032H60 (oiled Trishydroxyphenylmethane novolak resin such as ESN375, Naphthalene aralkyl novolac resin such as ESN375, Tetraphenylolethane 1031S (Yukaka Shell), YGD414S (Tohto Kasei), Trishydroxyphenylmethane EPPN502H (Nippon Kayaku) And glycidylamine type resins such as special bisphenol VG3101L (Mitsui Chemicals), special naphthol NC7000 (Nippon Kayaku), TETRAD-X, TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and the like.

  Moreover, the compound which has an epoxy group and a double bond and a triple bond in a molecule | numerator can also be mixed. Examples thereof include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether, propargyl glycidyl ether, glycidyl propionate, ethynyl glycidyl ether, and the like.

  In particular, among epoxy compounds, use of an epoxy compound having one epoxy group in the molecule is particularly desirable because it can suppress curing shrinkage during curing. As monofunctional epoxy compounds, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, alkyl monoglycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, pt-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, p -Sec-butylphenyl glycidyl ether, alkylphenol monoglycidyl ether, versatic acid monoglycidyl ester, linear alcohol monoglycidyl ether, glycerol monoglycidyl ether, polyglycol glycidyl ether, glycidyl methacrylate, etc. It is not a thing.

  Further preferred examples include pt-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, alkylphenol monoglycidyl ether, versatic acid monoglycidyl ester, linear alcohol monoglycidyl ether, glycerol monoglycidyl Ether, polyglycol glycidyl ether, 2-methylhexyl glycidyl ether, 3- (2-biphenyloxy) -1,2-epoxypropane, glycidyl 4-methoxyglycidyl ether, glycidyl mesityl ether, N- (2,3-epoxypropyl) ) Phthalimide, glycidyl hexadecyl ether, glycidyl nonyl phenyl ether, glycidyl lauryl ether, 3-dodecafluoroheproxy , 2-propoxide, Nippon Kayaku Co., Ltd. BR-250H, Nippon Kayaku Co., Ltd. BROC-Y, Nippon Kayaku Co., Ltd. BROC-C, Nippon Kayaku Co., Ltd. BROC, etc. can be illustrated. .

  The photosensitive resin composition of the present invention may contain a flame retardant in addition to the polyimide precursor, the (meth) acryl compound, and the photoinitiator.

  Next, the flame retardant used in the present invention will be described.

  When the flame retardant is a compound containing phosphorus, the phosphorus content is preferably 5.0% or more, more preferably 7.0% or more from the viewpoint that flame retardancy can be effectively imparted. When the flame retardant is a halogen-containing compound, the halogen content is preferably 15% or more, more preferably 20% or more from the viewpoint that flame retardancy can be effectively imparted. As halogen, those using chlorine or bromine are generally used. When the flame retardant is a compound containing a siloxane moiety, an organopolysiloxane compound containing an aromatic ring in a high ratio is preferable from the viewpoint of effectively imparting heat resistance and flame retardancy.

  When a phosphorus compound is used as a flame retardant, examples of the phosphorus compound include phosphazenes, phosphines, phosphine oxides, phosphoric acid esters (including condensed phosphoric acid esters), and phosphorous compounds such as phosphorous acid esters. From the aspect of compatibility with the polyimide comprising the polyimide precursor of the invention, phosphazene, phosphine oxide, or phosphate ester (including condensed phosphate ester) is preferable. The phosphorus content of the phosphorus compound used as a flame retardant is preferably 5.0% by weight, more preferably 7.0% by weight or more.

  Furthermore, from the point that it can impart flame retardancy and has hydrolysis resistance, for example, SPE-100 (phosphazene compound manufactured by Otsuka Chemical), SPH-100 (phosphazene compound manufactured by Otsuka Chemical), TPP (triphenyl phosphate). ), TCP (tricresyl phosphate), TXP (trixylenyl phosphate), CDP (cresyl diphenyl phosphate), PX-110 (cresyl 2,6-xylenyl phosphate) (all manufactured by Daihachi Chemical) Non-halogen-based condensed phosphate esters such as phosphate ester, CR-733S (resinol diphosphate), CR-741, CR-747, PX-200 (all manufactured by Daihachi Chemical), Biscoat V3PA (Osaka Organic Chemical) Kogyo), MR-260 (manufactured by Daihachi Chemical), etc. And phosphites such as triphenyl phosphite.

  When a halogen-containing compound is used as the flame retardant, the halogen content is preferably 30% by weight or more, more preferably 40% by weight or more, and most preferably 50% by weight or more. From the viewpoint of improving flame retardancy, the higher the halogen content, the better.

  Examples of the halogen-containing compound include chlorine-containing organic compounds and bromine-containing organic compounds. From the viewpoint of imparting flame retardancy, bromine-containing compounds are preferred, and the following can be exemplified.

  For example, brominated monomers such as New Frontier BR-30, BR-30M, BR-31, BR-42M (Daiichi Kogyo Seiyaku), brominated aromatic triazines such as Piroguard SR-245 (Daiichi Kogyo Seiyaku), Examples thereof include brominated aromatic polymers such as Pyroguard SR-250 and SR-400A (Daiichi Kogyo Seiyaku), and brominated aromatic compounds such as Piroguard SR-990A (Daiichi Kogyo Seiyaku).

  The flame retardant may be a phosphorus compound having a halogen atom in one molecule. Examples of such a compound include CLP (tris (2-chloroethyl) phosphate), TMCPP (tris (chloropropyl) phosphate), And halogen-containing phosphates such as CRP (tris (dichloropropyl) phosphate) and CR-900 (tris (tribromoneopentyl) phosphate) (both manufactured by Daihachi Chemical).

  Further, when a compound having a siloxane moiety is used as a flame retardant, it is preferably an organopolysiloxane compound containing a high proportion of aromatic rings from the viewpoint of imparting flame retardancy, and the phenyl group is a group of all organic substituents. Of these, an organopolysiloxane compound containing 10 mol% or more, more preferably 20 mol% or more, and more preferably 25 mol% or more is preferable. The smaller the phenyl group content, the smaller the flame retardant effect, and the higher the phenyl group content, the higher the flame retardant effect.

  When an organopolysiloxane compound having a low phenyl group content is used as a flame retardant, dispersibility and compatibility with the polyimide composition comprising the polyimide precursor of the present invention and a compound having an unsaturated carbon-carbon double bond When a heat resistant resin is formed into a film, only a low transparency film in which a plurality of components having different refractive indexes are phase-separated or an opaque film tends to be obtained. In addition, when such an organopolysiloxane compound having a low phenyl group content is used, it is difficult to obtain a sufficient flame retardant effect unless the amount added is increased, but the heat resistant resin composition produced when the amount added is increased. There is a tendency that physical properties such as mechanical strength of the material are significantly lowered.

  Furthermore, when an organopolysiloxane compound is used, flame retarding of the resin can be realized without generating harmful gases during combustion. In the case of a resin composition containing a halogen-containing compound, although flame retardancy can be realized, there is a drawback that harmful halogen-based gas is generated during combustion.

  The structure of the organopolysiloxane compound is generally composed of a combination of a trifunctional siloxane unit (T unit), a bifunctional siloxane unit (D unit), and a tetrafunctional siloxane unit (Q unit). A good combination in the present invention is a system containing a D unit such as a T / D system, a T / D / Q system, a D / Q system, and the like, and thereby provides good flame retardancy. In any combination, the D unit needs to be contained in an amount of 10 to 80 mol%. When the D unit is less than 10 mol%, the flexibility imparted to the organopolysiloxane compound is poor, and as a result, sufficient flame retardancy cannot be obtained. Moreover, when it exceeds 80 mol%, the dispersibility and solubility with (A) component: soluble polyimide will fall, and the external appearance and optical transparency and intensity | strength of a heat resistant resin composition will worsen. More preferably, the content of the D unit is in the range of 10 to 70 mol%. Therefore, according to the good D unit content, in the case of the T / D system, the content of the T unit is in the range of 30 to 90 mol%, and in the case of the T / D / Q system or the D / Q system, The content of T units is 0 to 89.99 mol%, preferably 10 to 79.99 mol%, and the content of Q units is 0.01 to 50 mol%. As long as the degree of freedom of space is secured, it is more advantageous to contain a larger amount of highly oxidized Q units in order to reproduce the flame retardancy. However, Q units in the organopolysiloxane compound are more advantageous. When the content exceeds 60 mol%, the inorganic fine particle property becomes too strong, and the dispersibility in the soluble polyimide becomes poor. Therefore, the blending amount needs to be kept below this. From the above siloxane unit content range, in consideration of the balance of flame retardancy, workability, molded product performance, etc., select a region where T units account for 40-80% by weight of the total weight of phenylsiloxane. It is further desirable to do so.

Here, when a preferable constituent siloxane unit is exemplified, the trifunctional siloxane unit (T unit) is C ₆ H ₅ SiO 3/2, CH ₃ SiO 3/2, and the bifunctional siloxane unit is (C ₆ H ₅ ) _{2. SiO2 / 2, (CH 3)} C 6 H 5 SiO2 / 2, a _{(CH 3) 2 SiO2 / 2} .

In this case, the dimethylsiloxane unit ((CH ₃ ) ₂ SiO2 / 2) as the D unit for imparting flexibility has the greatest effect of imparting flexibility to the silicone resin. Since flame retardancy tends to decrease, it is difficult to improve flame retardancy, and it is not desirable to contain a large amount. Accordingly, the dimethylsiloxane unit is preferably suppressed to 60 mol% or less in the D unit. The methylphenylsiloxane unit ((CH ₃ ) C ₆ H ₅ SiO2 / 2) is most preferred because it can impart flexibility and at the same time increase the phenyl group content. In addition, the diphenylsiloxane unit ((C ₆ H ₅ ) ₂ SiO2 / 2) is excellent in terms of maintaining a high phenyl group content, but since the bulky phenyl groups are densely packed on one Si, a large amount When combined, it brings a structure with a large steric hindrance to the organopolysiloxane molecule, so the spatial freedom of the siloxane skeleton is reduced, and the overlapping of aromatic rings required for the flame retardant mechanism by the coupling of aromatic rings to act May become difficult and may reduce the flame retarding effect. Therefore, the D unit may be used by blending these three raw materials so as to satisfy the above-mentioned range, but it is preferable to mainly use a methylphenylsiloxane unit.

  The weight average molecular weight of the flame retardant phenylsiloxane is preferably in the range of 300 to 50,000. A weight average molecular weight of less than 300 is not preferable because the heat resistant resin composition may ooze out in the B-stage state. If it exceeds 50,000, the solubility in the developer is lowered, the development time is prolonged, and the workability may be lowered. More preferably, it is the range of 400-30,000.

  Such an organopolysiloxane compound can be produced by a known method. For example, organochlorosilane and / or organoalkoxysilane that can form the above siloxane units by hydrolysis condensation reaction, or partially hydrolyzed condensate thereof, hydrolyze all hydrolyzable groups (chlor groups, alkoxy groups, etc.) For this purpose, excess water, the raw material silane compound and the resulting organopolysiloxane compound are mixed into a mixed solution of a dissolvable organic solvent and subjected to a hydrolysis condensation reaction. An organopolysiloxa compound having a desired weight average molecular weight can be obtained by adjusting the reaction temperature and time, the amount of water and an organic solvent. When using, unnecessary organic solvent may be removed and powdered for use.

  For example, KF50-100S, KF54, KF56, HIVAC F4, HIVAC F5, X-22-1824B, KR211 and KR311 manufactured by Shin-Etsu Silicone Co., Ltd. can be mentioned. Also good.

  The flame retardant is preferably used in an amount of 5 to 50% by weight based on the total amount of the polyimide composition comprising the polyimide precursor of the present invention and the compound having an unsaturated carbon-carbon double bond. If it is less than 5%, it tends to be difficult to impart flame retardancy to the coverlay film after curing, and if it exceeds 50%, the mechanical properties of the coverlay film after curing tend to be poor.

  In addition, when a halogen-containing compound is used as a flame retardant, antimony trioxide and / or antimony pentoxide is added, and the antimony oxide extracts halogen atoms from the flame retardant in the thermal decomposition start temperature range of the halogenated product. Since antimony is generated, the flame retardancy can be increased synergistically. The addition amount is preferably 0.1 to 10% by weight based on the total weight of the polyimide composition comprising the polyimide precursor of the present invention, the compound having an unsaturated carbon-carbon double bond, and the flame retardant, More preferably, it is 1 to 6% by weight.

  Since the antimony trioxide and antimony pentoxide white powders are not dissolved in an organic solvent, if the powder has a particle size of 100 μm or more, it becomes cloudy when mixed in the heat-resistant resin composition, making the resulting heat-resistant resin composition difficult. Although flame retardancy can be imparted, the transparency and developability tend to decrease, and therefore it is preferably 100 μm or less. Furthermore, in order to increase the flame retardancy without losing the transparency of the heat resistant resin composition, it is preferable to use antimony trioxide and / or antimony pentoxide having a powder particle size of 50 μm or less. More preferably, it is a powder having a particle size of 10 μm or less, most preferably a particle size of 5 μm or less.

  Examples of antimony pentoxide having a particle size of 50 μm or less include Sun Epoch NA-3181, NA-4800, NA-1030, NA-1070L (all manufactured by Nissan Chemical Industries).

  Antimony trioxide and / or antimony pentoxide may be mixed in the heat-resistant resin composition as a powder, or if the powder settles in the heat-resistant resin composition, the powder is dispersed in an organic solvent. Alternatively, it may be mixed after making into a sol form. As a specific method for forming a sol, a dispersant is added to an organic solvent together with an antimony trioxide and / or antimony pentoxide powder to form a network to prevent the powder from settling. As this dispersing agent, a mixture of vapor phase silica (silicon dioxide) and alumina (aluminum trioxide) can be used. The dispersant is preferably added in an amount of 2 to 5 times the weight of antimony trioxide and / or antimony pentoxide.

<Method for preparing photosensitive resin composition and method for preparing photosensitive dry film resist>
Then, the preparation method of the photosensitive resin composition and the preparation methods of the photosensitive dry film resist are demonstrated. The photosensitive dry film resist is produced by uniformly applying and drying an organic solvent solution of a photosensitive resin composition on a support film.

<Method for preparing photosensitive resin composition>
First, the preparation method of the photosensitive resin composition of this invention is demonstrated. The photosensitive resin composition of the present invention comprises (A) a polyimide precursor, (B) a (meth) acrylic compound having an unsaturated carbon-carbon double bond, (C) a photoreaction initiator, and, if necessary, other A solution in which the components are mixed at a certain ratio, and a solution in which the components are uniformly dissolved in an organic solvent is referred to as an organic solvent solution of the photosensitive resin composition. The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the components contained in the photosensitive resin composition. Examples of the organic solvent include ether solvents such as dioxolane, dioxane, and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, and alcohol solvents such as methyl alcohol and ethyl alcohol. These organic solvents may be used alone or in combination of two or more. In addition, since the organic solvent is removed in a later step, it is advantageous in terms of the manufacturing process to dissolve the components contained in the photosensitive resin composition and select one having the lowest boiling point as much as possible. .

<Method for producing photosensitive dry film resist>
Then, after apply | coating the organic solvent solution of said photosensitive resin composition uniformly on a support body film, a heating and / or hot air spray are performed. Thereby, the said organic solvent is removed and the photosensitive dry film resist in which the photosensitive resin composition became a film form can be obtained. The photosensitive dry film resist formed in this way is obtained by keeping the photosensitive resin composition in a semi-cured state (B stage). Therefore, when performing thermocompression bonding such as heat laminating, it has appropriate fluidity and can be suitably embedded in the pattern circuit of the printed wiring board. Moreover, after embedding a pattern circuit, it can be hardened completely by performing an exposure process, a thermocompression bonding process, and a heating cure.

  The temperature at which the organic solvent solution of the photosensitive resin composition is dried by performing the heating and / or hot air blowing has an unsaturated carbon-carbon double bond contained in the photosensitive resin composition (meta It is sufficient that the temperature is such that curable groups such as acrylic compounds do not react. Specifically, it is preferably 150 ° C. or lower, and particularly preferably 130 ° C. or lower. The drying time is preferably shorter as long as the organic solvent can be removed.

  The material for the support film is not particularly limited, but various commercially available films such as a polyethylene terephthalate (PET) film, a polyphenylene sulfide film, and a polyimide film can be used. Of the above support films, a PET film is often used because it has a certain degree of heat resistance and is relatively inexpensive. In addition, about the joint surface with the photosensitive dry film resist of a support body film, you may use what is surface-treated in order to improve adhesiveness and peelability.

  Furthermore, it is preferable to laminate a protective film on a photosensitive dry film resist prepared by applying a photosensitive resin composition to a support film and drying it. It is possible to prevent dust and dust in the air from adhering and prevent deterioration of quality due to drying of the photosensitive dry film resist.

  The protective film is preferably laminated and laminated on the photosensitive dry film resist surface at a temperature of 10 ° C to 50 ° C. In addition, when the temperature at the time of lamination processing becomes higher than 50 degreeC, the thermal expansion of a protective film will be caused and a wrinkle and a curl may arise in the protective film after a lamination process. In addition, since the said protective film peels at the time of use, it is preferable that the joint surface of a protective film and a photosensitive dry film resist has moderate adhesiveness at the time of storage, and is excellent in peelability.

  Although it does not specifically limit as a material of the said protective film, For example, a polyethylene film (PE film), a polyethylene vinyl alcohol film (EVA film), "the copolymer film of polyethylene and ethylene vinyl alcohol" (following ( "PE + EVA) copolymer film", "PE film and (PE + EVA) copolymer film laminate", or "(PE + EVA) copolymer and polyethylene film by simultaneous extrusion" (one side is PE film) And the other surface is a (PE + EVA) copolymer film surface).

  The PE film has the advantages of being inexpensive and having excellent surface slipperiness. Further, the (PE + EVA) copolymer film has appropriate adhesion to the photosensitive dry film resist and releasability. By using such a protective film, when a three-layer structure sheet having three layers of a protective film, a photosensitive dry film resist, and a support film is wound into a roll, the surface slipperiness is improved. Can do.

<Production of printed wiring board>
A method for producing a printed wiring board formed by forming the photosensitive dry film resist according to the present invention as an insulating protective layer will be described. The case where a CCL formed with a pattern circuit (hereinafter referred to as CCL with a circuit) is used as an example of the printed wiring board will be described as an example, but the same technique can be used when forming a multilayer printed wiring board. Thus, an interlayer insulating layer can be formed.

  First, the protective film is peeled from the three-layer structure sheet having the protective film, the photosensitive dry film resist, and the support film described above. Below, what peeled the protective film is described as the photosensitive dry film resist with a support film. Then, the CCL with a circuit is covered with the photosensitive dry film resist with a support film and bonded by thermocompression bonding so that the photosensitive dry film resist and the circuit portion of the CCL with circuit are opposed to each other. The bonding by thermocompression bonding may be performed by hot pressing, laminating (thermal laminating), hot roll laminating or the like, and is not particularly limited.

  When the bonding is performed by heat laminating or heat roll laminating (hereinafter referred to as laminating), the processing temperature may be equal to or higher than the lower limit temperature (hereinafter, pressure bonding possible) at which laminating is possible. . Specifically, the temperature at which the pressure bonding is possible is preferably within a range of 50 to 150 ° C., more preferably within a range of 60 to 120 ° C., and particularly preferably within a range of 80 to 120 ° C. preferable.

  When the said process temperature exceeds 150 degreeC, the crosslinking reaction of the photosensitive reactive group contained in the photosensitive dry film resist may arise at the time of a lamination process, and hardening of the photosensitive dry film resist may advance. On the other hand, when the processing temperature is lower than 50 ° C., the fluidity of the photosensitive dry film resist is low, and it becomes difficult to embed the pattern circuit. Furthermore, adhesiveness with the copper circuit of CCL with a copper circuit and the base film of CCL with a copper circuit may fall.

  By the above-described thermocompression treatment, a sample in which a photosensitive dry film resist is laminated on a CCL with a circuit and a support film is further laminated is obtained. Next, pattern exposure and development are performed on the bonded sample. In pattern exposure and development, a photomask pattern is placed on the support film of the bonded sample, and exposure processing is performed through the photomask. Thereafter, the support film is peeled off and development processing is performed, whereby holes (vias) corresponding to the photomask pattern are formed.

  In addition, although the said support body film is peeled off after exposure processing, even if it peels after the photosensitive dry film resist with support body film is bonded together on CCL with a circuit, ie, before performing an exposure process. Good. From the viewpoint of protecting the photosensitive dry film resist, it is preferable to peel off after the exposure process is completed.

  Here, the light source used for exposure is preferably a light source that effectively emits light of 300 to 430 nm. The reason for this is that the photoreaction initiator contained in the photosensitive dry film resist normally functions by absorbing light of 450 nm or less.

  Moreover, as a developing solution used for the development processing, a basic solution in which a basic compound is dissolved may be used. The solvent for dissolving the basic compound is not particularly limited as long as it is a solvent that can dissolve the basic compound, but water is particularly preferable from the viewpoint of environmental problems.

  Examples of the basic compound include hydroxides or carbonates of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate, and organic amines such as tetramethylammonium hydroxide. A compound etc. can be mentioned. 1 type may be used for the said basic compound and 2 or more types of compounds may be used for it.

  The concentration of the basic compound contained in the basic solution is preferably in the range of 0.1 to 10% by weight, but from the point of alkali resistance of the photosensitive dry film resist, 0.1 to 5% by weight. % Is more preferable.

  The development processing method is not particularly limited, and examples thereof include a method in which a development sample is placed in a basic solution and stirring, and a method in which a developer is sprayed onto the development sample.

  In the present invention, in particular, a developing process using a spray developing machine using a 1 wt% sodium hydroxide aqueous solution adjusted to a liquid temperature of 40 ° C. as a developer can be exemplified. Here, the spray developing machine is not particularly limited as long as it is an apparatus that sprays a developer on a sample.

  Here, the development time until the pattern of the photosensitive dry film resist can be drawn may be any time as long as the pattern can be drawn, but it is preferable that development is possible in a time of 180 seconds or less, and development is possible in a time of 90 seconds or less. It is most preferable that development can be performed in a time of 60 seconds or less. When the development time exceeds 180 seconds, productivity tends to be inferior.

  Here, as a measure of the development time, there is a method of measuring the dissolution time of the photosensitive dry film resist in the B stage (semi-cured) state. Specifically, a sample in which a photosensitive dry film resist is bonded to a glossy surface of a copper foil is unexposed and a 1 wt% sodium hydroxide aqueous solution (liquid temperature 40 ° C.) is used as a developer, spray pressure. In this method, spray development is performed at 0.85 MPa. By this spray development process, the photosensitive dry film resist is preferably dissolved and removed in a time of 180 seconds or less. When the time until the photosensitive dry film resist is dissolved and removed exceeds 180 seconds, workability tends to be lowered.

  After the exposure / development treatment is performed as described above, the photosensitive dry film resist is completely cured by heating and curing the photosensitive dry film resist. Thereby, the hardened photosensitive dry film resist becomes an insulating protective film of the printed wiring board.

  In addition, when forming a multilayer printed wiring board, the protective layer of the printed wiring board is used as an interlayer insulating layer, and after sputtering, plating, or bonding with a copper foil is further performed on the interlayer insulating layer Then, a pattern circuit may be formed and the photosensitive dry film resist may be laminated as described above. Thereby, a multilayer printed wiring board can be produced.

  In the present embodiment, the case where the photosensitive dry film resist is used as an insulating protective material or an interlayer insulating material for a printed wiring board has been described. However, the photosensitive dry film resist can be used for purposes other than the above.

  Examples are described below, but the present invention is not limited to these examples.

Example 1
1,2-ethanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as TMEG) (2,2′-bis (4-hydroxyphenyl) propane as a raw material for polyimide Dibenzoate) -3,3 ′, 4,4′-tetracarboxylic dianhydride (hereinafter referred to as ESDA), 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride (hereinafter referred to as “EDDA”) , BPADA), 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride (hereinafter referred to as DSDA), 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (Hereinafter referred to as BTDA), 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (hereinafter referred to as a-BPDA), bis [4- (3-aminophenoxy) phenyl] sulfone (hereinafter referred to as “a-BPDA”) , BAPS-M), silicone diamine (silicon diamine), diaminobenzoic acid, [bis (4-amino-3-carboxy) phenyl] methane (hereinafter referred to as MBAA), 2,2-bis (3-amino) -4-Hydroxyphenyl) hexafluoropropane (hereinafter referred to as 6FAP) was used. N, N′-dimethylformamide (DMF) and dioxolane were used as the solvent.

<Synthesis of acid dianhydride terminal oligomer: 1>
In a 2000 ml separable flask equipped with a stirrer, 16.22 g (150 mmol) of m-phenylenediamine and 180 g of DMF were taken and cooled and stirred. 172.95 g (300 mmol) of ESDA and 50 g of DMF were further added, and stirring was continued for 1 hour.
The reaction solution was placed in a vat and heated in a vacuum oven at 200 ° C. for 1 hour to obtain 180 g of acid dianhydride-terminated oligomer.

<Synthesis of polyimide precursor>
36.75 g of the above acid dianhydride terminal oligomer (corresponding to 30 mmol as acid dianhydride) and 17.30 g (30 mmol) of ESDA were dissolved in 70 g of DMF.

  A mixed solution of 49.8 g (60 mmol) of silicone diamine KF-8010 (manufactured by Shin-Etsu Silicone) and 21.34 g of DMF was added, and the mixture was stirred at room temperature for 1 hour. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. and 17.06 g (120 mmol) of glycidyl methacrylate were added, and the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried in a vacuum oven at 45 ° C. to obtain 101 g of a polyimide precursor.

^The amount of glycidyl methacrylate introduced was measured by ¹ H-NMR. A Varian Gemini 300 operating frequency of 300 Hz was used and dissolved in the solvent DMSO-d ₆ to a concentration of 1%. The amount of glycidyl methacrylate introduced was determined from the signal of δ6.8 to 8.6 derived from the aromatic ring and the signal ratio in the vicinity of δ6.1 derived from CH =. It was found that the amount introduced was 20% of the total carboxylic acid of the amic acid.

  The molecular weight was measured using a high-speed GPC (trade name HLC-8220GPC, manufactured by Tosoh Corporation). The measurement conditions were DMF (0.036M LiBr, 0.019M phosphoric acid included) as a developing solvent, a column manufactured by Shodex, trade name: KD-805-M, a column temperature of 40 ° C., and a detector. PI (PEO standard) was used, and the flow rate was 0.6 ml / min. As a result, the weight average molecular weight was 50000, the number average molecular weight was 20000, and the weight average molecular weight / number average molecular weight was 2.5.

<Evaluation of polyimide precursor: migration resistance>
Line / space = 50/50 μm shown in FIG. 1 on Nippon Steel Chemical's flexible copper-clad laminate (single-sided copper-clad laminate having a copper foil on one side of a polyimide resin: SC18-25-00FR) A comb pattern was formed.

  The polymide precursor solution was applied to the comb pattern using a bar coater and heated at 90 ° C. for 10 minutes, 120 ° C. for 10 minutes, and 170 ° C. for 1 hour to remove the organic solvent to obtain a laminate.

  In an environmental tester at 85 ° C. and 85% RH, a DC voltage of 60 V was applied to both terminals of the coated comb pattern, and changes in resistance value and presence / absence of migration were observed.

Migration resistance showed a resistance value of 500 ^-6 or more and 10 ⁻⁶ Ω or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.

(Comparative Example 1)
3.24 g (30 mmol) of m-phenylenediamine, 49.8 g (60 mmol) of KF-8010 (manufactured by Shin-Etsu Silicone) and 130 g of DMF were placed in a reaction vessel, and 51.89 g (90 mmol) of ESDA was added thereto, followed by stirring for 1 hour. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. and 17.06 g (120 mmol) of glycidyl methacrylate were added, and the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried in a vacuum oven to obtain 98 g of a polyimide precursor.

  In the same manner as in Example 1, the amount of glycidyl methacrylate introduced was determined. It was found that the amount introduced was 22% of the total carboxylic acid of the amic acid.

  When this polyamic acid solution was measured under the same conditions as in Example 1, the weight average molecular weight was 53,000, the number average molecular weight was 19,600, and the weight average molecular weight / number average molecular weight was 2.70.

<Evaluation of polyimide precursor: migration resistance>
When migration resistance was evaluated in the same manner as in Example 1, a short circuit occurred in 50 hours, and dendrites were formed. Therefore, it was confirmed that imidation was not completed in 170 ° C. imidization.

(Example 2)
<Synthesis of acid dianhydride terminal oligomer>
To a 500 ml separable flask equipped with a stirrer, 41.64 g (80 mmol) of BPADA and 100 g of DMF were added and stirred while cooling with ice. 14.65 g (40 mmol) of 6FAP was dissolved in 50 g of DMF, added to the vessel, and stirred for 1 hour. The reaction solution was placed in a vat and heated in a vacuum oven at 190 ° C. for 1 hour to obtain 54 g of acid dianhydride-terminated oligomer.

<Synthesis of polyimide precursor>
The above acid dianhydride terminal oligomer 41.14 g (corresponding to 30 mmol as acid dianhydride) was dissolved in 82.5 g of dioxolane. A mixed solution of 24.9 g (30 mmol) of silicone diamine KF-8010 (manufactured by Shin-Etsu Silicone) and 16.6 g of dioxolane was added and stirred at room temperature for 2 hours. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. and 17.06 g (120 mmol) of glycidyl methacrylate were added, and the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried in a vacuum oven to obtain 60 g of a polyimide precursor.

  In the same manner as in Example 1, the amount of glycidyl methacrylate introduced was determined. It was found that the amount introduced was 25% of the total carboxylic acid of the amic acid.

  The polyimide precursor solution was measured under the same conditions as in Example 1. As a result, the weight average molecular weight was 45,000, the number average molecular weight was 17000, and the weight average molecular weight / number average molecular weight was 2.65.

<Evaluation of polyimide precursor: migration resistance>
When migration resistance was evaluated in the same manner as in Example 1, the migration resistance showed a resistance value of 500 ^-6 Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.

<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acryl compound having an unsaturated carbon-carbon double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate made by Kyoeisha Chemical Co., Ltd. NP-4EA 15 parts by weight, and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) and others : Otsuka Chemical Co., Ltd. phosphazene compound SPE-100 10 parts by weight (adhesiveness)
The heat-resistant resin composition solution was applied to a polyimide film Apical 25NPI (manufactured by Kaneka Chemical Co., Ltd.) so that the thickness after drying was 25 microns, dried at 90 ° C. for 5 minutes, and electrolytic copper foil (Mitsui Metals 3EC The rough surface of -VLP (1 ounce) was aligned with the heat resistant resin composition side, laminated under conditions of 110 ° C. and 20000 Pa · m, and heated at 160 ° C. for 2 hours to obtain a laminate. This laminate was made according to the peel strength (90 degrees) of JIS C 6481. However, the width was measured at a width of 3 mm and converted to 1 cm. The adhesive strength was 5.8 N / cm.

(Solder heat resistance)
The heat-resistant resin composition solution was applied to the bright surface of electrolytic copper foil (Mitsui Metals 3EC-VLP 1 ounce) so that the thickness after drying was 25 microns, dried at 90 ° C. for 5 minutes, and heated at 160 ° C. for 2 hours. To obtain a laminate. This laminate was conditioned at 40 ° C. and 95% RH for 24 hours, then immersed in a solder bath for 10 seconds, and the presence or absence of surface swelling and discoloration was observed. The highest temperature that did not cause blistering or discoloration was defined as the solder heat resistance temperature. The solder heat resistance temperature was 280 ° C.

(Photosensitivity)
The photosensitive resin composition solution prepared above was applied onto a PET film (thickness 25 μm) so that the thickness after drying was 25 μm, dried at 90 ° C. for 2 minutes to remove the organic solvent, and photosensitive. A dry film resist was used.

  The photosensitive resin composition surface of the photosensitive dry film resist was laminated on the bright surface of electrolytic copper foil (3EC-VLP 1 ounce made by Mitsui Metals) and laminated at 100 ° C. and 20000 Pa · m while being shielded from light to obtain a laminate. .

A mask pattern was placed on the laminate, and 400 nm light was exposed by 300 mJ / cm ² and developed with a 1 wt% aqueous sodium hydroxide solution (liquid temperature 40 ° C.). The photomask pattern is drawn with minute holes of 500 μmφ, 200 μmφ, and 100 μmφ and lines with a line / space of 500 μm / 500 μm, 200 μm / 200 μm, and 100 μm / 100 μm. The pattern formed by development was then washed with distilled water to remove the developer.

  Fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.

(Migration resistance of photosensitive resin)
Line / space = 50/50 μm shown in FIG. 1 on Nippon Steel Chemical's flexible copper-clad laminate (single-sided copper-clad laminate having a copper foil on one side of a polyimide resin: SC18-25-00FR) A comb pattern was formed.

On the comb pattern, the photosensitive dry film resist prepared above was laminated and laminated under conditions of 100 ° C. and 20000 Pa · m. The film was exposed to 400 nm light by 400 mJ / cm ² and then heated at 180 ° C. for 2 hours for lamination.

  In an environmental tester at 85 ° C. and 85% RH, a DC voltage of 60 V was applied to both terminals of the coated comb pattern, and changes in resistance value and presence / absence of migration were observed.

Migration resistance showed a resistance value of 500 ^-6 or more and 10 ⁻⁶ Ω or more, and no dendrite was observed.

(Comparative Example 2)
6FAP 10.99 g (30 mmol), KF-8010 (manufactured by Shin-Etsu Silicone) 24.9 g (30 mmol) and dioxolane g were placed in a reaction vessel, and BPADA 31.23 g (60 mmol) was added and stirred for 1 hour to obtain a polyamic acid solution. . When this polyamic acid solution was measured under the same conditions as in Example 1, the weight average molecular weight was 48,000, the number average molecular weight was 17000, and the weight average molecular weight / number average molecular weight was 2.82.

<Evaluation of polyimide precursor: migration resistance>
When migration resistance was evaluated in the same manner as in Example 1, a short circuit occurred in 50 hours, and dendrites were formed. Therefore, it was confirmed that imidation was not completed in 170 ° C. imidization.

<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a solid content concentration of 30% by weight. (The mixing ratio is the same as in Example 2)
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acryl compound having an unsaturated carbon-carbon double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate made by Kyoeisha Chemical Co., Ltd. NP-4EA 15 parts by weight, and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) and others : Otsuka Chemical Co., Ltd. phosphazene compound SPE-100 10 parts by weight Each part was evaluated in the same manner as in Example 2.

(Adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 1.5 N / cm.
(Solder heat resistance)
When the solder heat resistance temperature was measured in the same manner as in Example 2, the solder heat resistance temperature was 230 ° C.

(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, the pattern flowed with the developer, and the pattern could not be drawn.

(Migration resistance of photosensitive resin)
When migration resistance was evaluated in the same manner as in Example 2, the migration resistance was short-circuited in 40 hours, and dendrites were observed.

(Example 3)
<Synthesis of acid dianhydride terminal oligomer>
To a 500 ml separable flask equipped with a stirrer, 41.64 g (80 mmol) of BPADA and 100 g of DMF were added and stirred while cooling with ice. The compound 19.79 (40 mmol) represented by the formula (12) was dissolved in 50 g of DMF, added to the vessel, and stirred for 1 hour. The reaction solution was placed in a vat and heated in a vacuum oven at 190 ° C. for 1 hour to obtain 59.0 g of an acid dianhydride-terminated oligomer.

＜ポリイミド前駆体の合成＞
上記の酸二無水物末端オリゴマー４４．９９ｇ（酸二無水物として３０ｍｍｏｌに相当）とＥＳＤＡ１７．３０ｇ（３０ｍｍｏｌ）をジオキソラン１３５ｇに溶解した。シリコーンジアミンＫＦ−８０１０（信越シリコーン製）４９．８ ｇ （６０ｍｍｏｌ）とジオキソラン３３．２ｇの混合溶液を加え、２時間室温で撹拌を行った。次いで、トリエチルアミン０．６ｇ、和光純薬株式会社製Ｑ−１３０１ ２００ｍｇ、２−シソシアナトエチルメタクリレート６．２ｇ（４０ｍｍｏｌ）を加え、６０℃で２時間撹拌を行った。反応終了後、反応溶液をイソプロピルアルコールに投入し、沈殿した樹脂を、真空オーブンで乾燥して、９８ｇのポリイミド前駆体を得た。

<Synthesis of polyimide precursor>
The above acid dianhydride terminal oligomer 44.99 g (corresponding to 30 mmol as acid dianhydride) and 17.30 g (30 mmol) of ESDA were dissolved in 135 g of dioxolane. A mixed solution of 49.8 g (60 mmol) of silicone diamine KF-8010 (manufactured by Shin-Etsu Silicone) and 33.2 g of dioxolane was added, and the mixture was stirred at room temperature for 2 hours. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd., and 6.2 g (40 mmol) of 2-isocyanocyanatoethyl methacrylate were added, and the mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried in a vacuum oven to obtain 98 g of a polyimide precursor.

  In the same manner as in Example 1, the amount of 2-sisocyanatoethyl methacrylate introduced was determined. As for the introduction amount, it was found that 2-sisocyanatoethyl methacrylate was introduced at a ratio of 0.25 to one acid dianhydride.

  The polyimide precursor solution was measured under the same conditions as in Example 1. As a result, the weight average molecular weight was 55000, the number average molecular weight was 19000, and the weight average molecular weight / number average molecular weight was 2.89.

<Evaluation of polyimide precursor>
When migration resistance was evaluated in the same manner as in Example 1, the migration resistance showed a resistance value of 500 ^-6 Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.

<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acryl compound having an unsaturated carbon-carbon double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate made by Kyoeisha Chemical Co., Ltd. NP-4EA 15 parts by weight, and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) and others : Otsuka Chemical Co., Ltd. phosphazene compound SPE-100 10 parts by weight (adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 6.8 N / cm.

(Solder heat resistance)
When the solder heat resistance temperature was measured by the same method as in Example 2, the solder heat resistance temperature was 280 ° C.

(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.

(Migration resistance of photosensitive resin)
When the migration resistance was evaluated in the same manner as in Example 2, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

Example 4
<Synthesis of acid dianhydride terminal oligomer>
To a 500 ml separable flask equipped with a stirrer, 41.64 g (80 mmol) of BPADA and 100 g of DMF were added and stirred while cooling with ice. 4.56 g (40 mmol) of 3,5-diaminobenzoic acid was dissolved in 50 g of DMF, added to the vessel and stirred for 1 hour. The reaction solution was placed in a vat and heated in a vacuum oven at 190 ° C. for 1 hour to obtain 43.0 g of acid dianhydride-terminated oligomer.

<Synthesis of polyimide precursor>
33.57 g of the above acid dianhydride-terminated oligomer (corresponding to 30 mmol as acid dianhydride) was dissolved in 70 g of dioxolane. A mixed solution of 24.9 g (30 mmol) of silicone diamine KF-8010 (manufactured by Shin-Etsu Silicone) and 16.6 g of dioxolane was added, and the mixture was stirred at room temperature for 2 hours. Next, 0.6 g of triethylamine, 200 mg of Q-1301 manufactured by Wako Pure Chemical Industries, Ltd. and 11.37 g (80 mmol) of glycidyl methacrylate were added, and the mixture was stirred at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was poured into isopropyl alcohol, and the precipitated resin was dried in a vacuum oven to obtain 50 g of a polyimide precursor.

  In the same manner as in Example 1, the amount of glycidyl methacrylate introduced was determined. It was found that the amount introduced was 20% of the total carboxylic acid of the amic acid.

  The polyimide precursor solution was measured under the same conditions as in Example 1. As a result, the weight average molecular weight was 55000, the number average molecular weight was 19000, and the weight average molecular weight / number average molecular weight was 2.89.

<Evaluation of polyimide precursor>
When migration resistance was evaluated in the same manner as in Example 1, the migration resistance showed a resistance value of 500 ^-6 Ω or more for 500 hours or more, and no dendrite was observed. Therefore, it was confirmed that imidization was completely completed by imidization at 170 ° C.

<Adjustment of photosensitive resin composition>
The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acryl compound having an unsaturated carbon-carbon double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate made by Kyoeisha Chemical Co., Ltd. NP-4EA 15 parts by weight, and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (E) and others : Otsuka Chemical Co., Ltd. phosphazene compound SPE-100 10 parts by weight (adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 6.8 N / cm.

(Solder heat resistance)
When the solder heat resistance temperature was measured by the same method as in Example 2, the solder heat resistance temperature was 280 ° C.

(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, fine holes and lines / spaces of 100 μmφ could be drawn up to 100 μm / 100 μm.

(Migration resistance of photosensitive resin)
When the migration resistance was evaluated in the same manner as in Example 2, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

(Example 5)
In the same manner as in Example 5, except that methacrylic acid-2-dimethylaminoethyl ester was added as component (D).

The following components were mixed to prepare a dioxolane solution with a solid content concentration of 30% by weight.
(A) 49 parts by weight of the polyimide precursor synthesized above (B) (meth) acryl compound having an unsaturated carbon-carbon double bond 10 parts by weight of Osaka Organic Chemical Co., Ltd. V # 2308 Light acrylate made by Kyoeisha Chemical Co., Ltd. NP-4EA 15 parts by weight and Dai-ichi Kogyo Seiyaku Co., Ltd. BR-42M 15 parts by weight (C) Photoinitiator bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide 1 part by weight (D) methacryl Acid-2-dimethylaminoethyl ester 10 parts (E) Other: Otsuka Chemical Co., Ltd. Phosphazene Compound SPE-100 10 parts by weight (adhesiveness)
When the adhesive strength was measured in the same manner as in Example 2, the adhesive strength was 6.8 N / cm.

(Solder heat resistance)
When the solder heat resistance temperature was measured by the same method as in Example 2, the solder heat resistance temperature was 280 ° C.

(Photosensitivity)
When the photosensitivity was evaluated in the same manner as in Example 2, fine holes and lines / spaces of 100 μmφ could be drawn up to 70 μm / 70 μm.

(Migration resistance of photosensitive resin)
When the migration resistance was evaluated in the same manner as in Example 2, the migration resistance showed a resistance value of 500 ⁻¹⁰ Ω or more for 500 hours or more, and no dendrite was observed.

Comb pattern (line / space = 50μm / 50μm)

Claims (10)

A polyimide precursor having both an imide structure represented by formula (1) and an amic acid structure represented by formula (2);
A polyimide precursor obtained by reacting a compound having both an unsaturated carbon-carbon double bond and an epoxy group in the molecule and / or a compound having both an unsaturated carbon-carbon double bond and an isocyanate group in the molecule body.

(Wherein R ¹ represents a tetravalent organic group, R ² represents a divalent organic group obtained by removing an amino group from a diamine, or a divalent organic group obtained by removing an isocyanate group from a diisocyanate, and R ³ represents a formula ( 3), R ⁴ represents any one of a methyl group, an ethyl group, and a phenyl group, and x = 2 to 10 and y = 4 to 30.)

^2. The polyimide precursor according to claim 1, wherein in the formula (1), a part of R ² represents a divalent organic group obtained by removing an amino group from a diamine having a hydroxyl group and / or a carboxyl group. The polyimide precursor according to claim 2, wherein a part of R ² in the formula (1) is the formula (4).

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , m is 0 to 3 is shown.) The polyimide precursor according to claim 2, wherein a part of R ² in the formula (1) is the formula (5).

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , n is 1 to 5 is shown.) In the formula (1), the polyimide precursor according to claim 2, wherein the portion of R ² is the formula (6).

(R ⁵ is —, — (C═O) —, —C (CH ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —O—, —C (CF ₃ ) ₂ —, —CH (CH ₃ )-, -C (CH ₃ ) (CH ₂ CH ₃ )-, cyclohexyl, R ⁶ and R ⁷ are H, CH _3- , CH ₃ CH _2- , r is 0 to 5 is shown.) (A) In addition to 100 parts by weight of the polyimide precursor according to any one of claims 1 to 5, (B) 1 to 400 parts by weight of a (meth) acrylic compound having an unsaturated carbon-carbon double bond is an essential component. A photosensitive resin composition. In addition to the photosensitive resin composition according to claim 6, (C) a photoreaction initiator is 0.01 to 50 weights with respect to 100 parts by weight of the polyimide precursor according to any one of claims 1 to 5. A photosensitive resin composition containing a part as an essential component. In addition to the photosensitive resin composition according to claim 7, with respect to 100 parts by weight of the polyimide precursor according to claim 1,
(D) 0.01 to 30 parts by weight of a compound having an ethylenically unsaturated carbon-carbon double bond and a tertiary amino group in the molecule or a compound having an ethylenically unsaturated carbon-carbon double bond and an amide group A photosensitive resin composition as an essential component. The photosensitive resin composition according to any one of claims 6 to 8, wherein the polyimide precursor according to any one of claims 1 to 5 is dehydrated and closed to form a polyimide. A photosensitive dry film resist comprising the photosensitive resin composition according to claim 9.

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