JP6738353B2 - Photosensitive resin composition, dry film, cured product and printed wiring board - Google Patents

Description

The present invention relates to a photosensitive resin composition, a dry film, a cured product and a printed wiring board.

Polyimide is widely applied to various fields based on its excellent properties such as high insulation, heat resistance, and high mechanical strength. For example, the application is not limited to the aerospace field, which was first applied, and is being applied to coating films for semiconductor elements, flexible printed wiring boards, and heat-resistant insulating interlayer materials.

Polyimide has the aspect that it has poor thermoplasticity and poor solubility in organic solvents and is difficult to process. Therefore, the polyimide, a photosensitive resin composition obtained by blending a polyimide precursor and a photoreactive compound such as polyamic acid or polyamic acid ester, a desired pattern film by developing after irradiation with actinic rays After being formed, it is widely used by a method of applying a high temperature to close the ring to imidize it (for example, Patent Documents 1 and 2).

For example, Patent Document 1 describes a photosensitive resin composition containing a polyamic acid ester and a photosensitive base generator. Further, Patent Document 2 describes a negative photosensitive resin composition containing a polyamic acid derivative containing both an amic acid moiety and an amic acid ester moiety and a compound that generates a basic substance upon irradiation with radiation.

JP-A-5-197148 JP, 2003-084435, A

In recent years, further miniaturization of the polyimide pattern film has been required with the advancement of semiconductor packaging technology and the increase in density.

Therefore, an object of the present invention is to provide a photosensitive resin composition having excellent resolution, a dry film having a resin layer obtained from the composition, a cured product of the composition or a resin layer of the dry film, and the cured product. It is to provide a printed wiring board having an object.

As a result of intensive studies in view of the above, the present inventors have found that the above problems can be solved by using a polyamic acid ester having a specific structure, and have completed the present invention.

（式（１）中、Ｒ_１は４価の有機基であり、Ｒ_２は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、Ｘは２価の有機基であり、Ｒ_３およびＲ_４は、相互に同一でも異なってもよく、１価の有機基またはケイ素を有する官能基であり、ｍは１以上の整数であり、ｎは０または１以上の整数である。）
なお、本発明の感光性樹脂組成物における（Ａ）ポリアミック酸エステルは、実質的にアミック酸部分を含まない。即ち、本発明の感光性樹脂組成物における（Ａ）ポリアミック酸エステルは、特開２００３−０８４４３５号公報に記載されているような、アミック酸部分およびアミック酸エステル部分の両方を含むポリアミド酸誘導体とは異なるものである。That is, the photosensitive resin composition of the present invention is a photosensitive resin composition containing (A) a polyamic acid ester and (B) a photobase generator, wherein the (A) polyamic acid ester is It has a structure represented by the following general formula (1).

(In the formula (1), R ₁ is a tetravalent organic group, R ₂ is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group. X is a divalent organic group, R ₃ and R ₄ , which may be the same or different from each other, are a monovalent organic group or a functional group having silicon, and m is 1 or more. It is an integer, and n is an integer of 0 or 1 or more.)
The (A) polyamic acid ester in the photosensitive resin composition of the present invention contains substantially no amic acid moiety. That is, the (A) polyamic acid ester in the photosensitive resin composition of the present invention is a polyamic acid derivative containing both an amic acid moiety and an amic acid ester moiety, as described in JP 2003-084435 A. Is different.

In the photosensitive resin composition of the present invention, R ₁ in the general formula (1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an alicyclic group. It is preferably a tetravalent organic group containing a hydrocarbon group or a tetravalent organic group containing a fluorine atom.

（式（１−１）中、Ｒ_２は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、Ｘは２価の有機基であり、Ｒ_３およびＲ_４は、相互に同一でも異なってもよく、１価の有機基またはケイ素を有する官能基であり、ｍは１以上の整数であり、ｎは０または１以上の整数である。）

（式（１−２）中、
Ｒ_２は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、
Ｘは２価の有機基であり、
Ｒ_３およびＲ_４は、相互に同一でも異なってもよく、１価の有機基またはケイ素を有する官能基であり、
ｍは１以上の整数であり、
ｎは０または１以上の整数である。）In the photosensitive resin composition of the present invention, the (A) polyamic acid ester preferably has a structure represented by at least one of the following general formulas (1-1) and (1-2).

(In the formula (1-1), R ₂ is any one of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group, and X is a divalent group. R ₃ and R ₄ , which may be the same or different from each other, are monovalent organic groups or functional groups having silicon, m is an integer of 1 or more, and n is 0 or 1 It is the above integer.)

(In formula (1-2),
R ₂ is any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group,
X is a divalent organic group,
R ₃ and R ₄ , which may be the same or different from each other, are a monovalent organic group or a functional group having silicon,
m is an integer of 1 or more,
n is 0 or an integer of 1 or more. )

In the photosensitive resin composition of the present invention, the (B) photobase generator is preferably an ionic photobase generator.

The dry film of the present invention is characterized by having a resin layer obtained by applying the photosensitive resin composition to a film and drying the film.

The cured product of the present invention is characterized by being obtained by curing the photosensitive resin composition or the resin layer of the dry film.

The printed wiring board of the present invention is characterized by having the cured product.

According to the present invention, a photosensitive resin composition having excellent resolution, a dry film having a resin layer obtained from the composition, a cured product of the composition or a resin layer of the dry film, and the cured product It is possible to provide a printed wiring board having.

Hereinafter, the components contained in the photosensitive resin composition of the present invention will be described in detail.

（式（１）中、Ｒ_１は４価の有機基であり、Ｒ_２は脂環式骨格を有する基、フェニレン基、アルキレン基で結合されたビスフェニレン骨格を有する基、および、アルキレン基のいずれかであり、Ｘは２価の有機基であり、Ｒ_３およびＲ_４は、相互に同一でも異なってもよく、１価の有機基またはケイ素を有する官能基であり、ｍは１以上の整数であり、ｎは０または１以上の整数である。）[(A) Polyamic acid ester]
The (A) polyamic acid ester used in the present invention has a structure represented by the following general formula (1).

(In the formula (1), R ₁ is a tetravalent organic group, R ₂ is a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group. X is a divalent organic group, R ₃ and R ₄ , which may be the same or different from each other, are a monovalent organic group or a functional group having silicon, and m is 1 or more. It is an integer, and n is an integer of 0 or 1 or more.)

The number average molecular weight of the (A) polyamic acid ester is preferably 1,000 to 1,000,000, more preferably 5,000 to 500,000, and even more preferably 10,000 to 200,000.

In the formula (1), the tetravalent organic group represented by R ₁ is not particularly limited and may be selected according to the application. Examples thereof include an aromatic group, preferably an aromatic group having 6 to 32 carbon atoms, or an aliphatic group, preferably an aliphatic group having 4 to 20 carbon atoms. R ₁ is preferably a substituent R ₁ contained in the below-mentioned acid dianhydride used in the production of the (A) polyamic acid ester.

When forming a pattern film using a photosensitive resin composition with short-wavelength light, it is preferable to use an aliphatic group as R ₁ from the viewpoint of the absorption characteristics of the polymer.

In the present invention, particularly from the viewpoint of resolution, R ₁ is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, an aromatic group and an alicyclic hydrocarbon group. It is preferable that it is a tetravalent organic group containing or a tetravalent organic group containing a fluorine atom.

のうちのいずれか１種で表されることが好ましい。The tetravalent organic group containing a condensed ring of the aromatic ring and the aliphatic hydrocarbon ring in R ₁ is

It is preferably represented by any one of the above.

Formula (1-1):
Z ₁ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with an ethylene group which is common to Z _2. Is at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxy group and a halogen atom as a substituent. You may have.

Z ₂ is an aliphatic carbon atom having 3 to 10 carbon atoms (preferably 4 to 6, especially 4) which forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon) with an ethylene group common to Z _1. It is a hydrogen group, and the aliphatic hydrocarbon ring has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 6 carbon atoms) as a substituent. 10), a hydroxy group, or a halogen atom. Two monovalent bonds represented by “-” (ie, a set of bonds, a bond on the right side of Z ₂ ) are bonded to carbons adjacent to each other, but “=CR ₆ The divalent bond represented by "-" is preferably bonded to the carbon atom adjacent to the adjacent carbon atom to which the two "-" bonds are bonded or the carbon atom adjacent thereto. The latter is particularly preferable. For example, when the aliphatic hydrocarbon ring is a cyclohexane ring, two “—” bonds are bonded to the 3,4 position, and “=CR ₆ —” is added to the 2 or 1 position (preferably to the 1 position). It is preferably bound. R ₆ is generally a hydrogen atom, an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxy group or a halogen atom, and preferably a hydrogen atom.

Formula (1-2):
Z ₃ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with an ethylene group common to Z ₄ ; Is at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxy group and a halogen atom as a substituent. You may have.

Z ₄ is an aliphatic carbon atom having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4) which forms an aliphatic hydrocarbon ring (alicyclic hydrocarbon) with an ethylene group common to Z _3. It is a hydrogen group, and the aliphatic hydrocarbon ring has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 6 carbon atoms) as a substituent. 10), a hydroxy group, or a halogen atom. Two "-" monovalent bond represented by (a pair of bond, the right set of bond or left set of bonds of Z ₄₎ is attached to the carbon adjacent respectively However, a pair of bonds may be arranged adjacent to each other, or if the ring is large, at least one carbon atom may be arranged mutually.

Formula (1-3):
Z ₅ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) together with an ethylene group common to Z ₆ and is an aromatic ring. Is at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxy group and a halogen atom as a substituent. You may have. Two monovalent bonds represented by "-" are bonded to adjacent carbons, but combinations of adjacent monovalent bonds represented by two "-" are also adjacent to each other. Or if the ring is large, they may be arranged at least one carbon atom apart from each other. Two "-" monovalent bond represented by is bonded to adjacent carbon "= CR 7 _-" divalent bonding hand represented by the "-" bonds of It is preferable that at least one carbon atom of the carbon to which is bonded is bonded to the adjacent carbon atom. R ₇ is generally a hydrogen atom, an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxy group or a halogen atom, and a hydrogen atom is preferable.

Z ₆ is a fat having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4) forming an aliphatic hydrocarbon ring (ring of alicyclic hydrocarbon) with an ethylene group common to Z _5. It is a group hydrocarbon hydrocarbon, and the saturated hydrocarbon ring has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 carbon atoms) as a substituent. It may have a hydroxy group or a halogen atom.

Formula (1-4):
Z ₇ is an unsaturated hydrocarbon group having 4 to 12 carbon atoms which forms an aromatic ring (preferably a benzene ring, a naphthalene ring, especially a benzene ring) with an ethylene group common to Z ₈ and is an aromatic ring. Is at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 10 carbon atoms), a hydroxy group and a halogen atom as a substituent. You may have. Two "-" monovalent bond represented by (right bond Z ₇ or the left bond of Z ₇₎ is bonded to the carbon adjacent each pair of The bonds may be arranged adjacent to each other, or if the ring is large, they may be arranged at least one carbon atom apart from each other.

Z ₈ is a saturated group having 3 to 10 carbon atoms (preferably 4 to 6, particularly 4) forming an aliphatic hydrocarbon ring (ring of alicyclic hydrocarbon) together with an ethylene group common to Z _7. It is a hydrocarbon group, and the saturated hydrocarbon ring has at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), an aryl group (having 6 to 6 carbon atoms) as a substituent. 10), a hydroxy group, or a halogen atom.

Among the formulas (1-1) to (1-4), the organic groups represented by the formulas (1-1) and (1-2) are preferable, and the organic group represented by the formula (1-1) is particularly preferable. preferable.

The tetravalent organic group containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthalene group, especially a phenyl group), and preferably has a trifluoromethyl group and an aromatic group.

（式（１−１）中、Ｒ_２〜Ｒ_４、Ｘ、ｍおよびｎは式（１）と同様である。）

（式（１−２）中、Ｒ_２〜Ｒ_４、Ｘ、ｍおよびｎは式（１）と同様である。）The (A) polyamic acid ester preferably has a structure represented by at least one of the following general formulas (1-1) and (1-2).

(In the formula (1-1), R _{2 to} R ₄ , X, m and n are the same as those in the formula (1).)

(In the formula (1-2), R _{2 to} R ₄ , X, m and n are the same as those in the formula (1).)

In the present invention, R ₂ in the formula (1) is any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group. The phenylene group and the alkylene group are directly bonded to the two nitrogen atoms bonded to R ₂ in formula (1). On the other hand, the alicyclic skeleton and the bisphenylene skeleton bonded by the alkylene group may or may not be directly bonded to the two nitrogen atoms bonded to R ₂ in the formula (1). R ₂ is preferably a substituent R ₂ contained in the below-mentioned diamine or diisocyanate used in the production of the (A) polyamic acid ester.

（式（２−１）中、ｎ１は０〜１０の整数を表し、Ｒ_１０は脂肪族基であり、好ましくは炭素数１〜５のアルキレン基であり、より好ましくはメチレン基を表し、Ｒ_１１はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表す。）The group having the alicyclic skeleton in R ₂ may have a substituent and may form a condensed ring. The group having an alicyclic skeleton is preferably represented by the following general formula (2-1).

(In the formula (2-1), n1 represents an integer of 0 to ₁₀ , R ₁₀ represents an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, R 10 ₁₁ is each independently an aliphatic group or an aromatic group, preferably an aliphatic group such as a methyl group or an ethyl group.)

（式（２−２）中、ｎ２は０〜４の整数を表し、Ｒ_１２はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表す。）The phenylene group for R ₂ may have a substituent and may form a condensed ring. The phenylene group is preferably represented by the following general formula (2-2).

(In the formula (2-2), n2 represents an integer of 0 to 4 and R _12's each independently represent an aliphatic group or an aromatic group, preferably a methyl group, an ethyl group or the like. .)

（式（２−３）中、ｎ３およびｎ４はそれぞれ独立に０〜４の整数を表し、Ｒ_１３およびＲ_１４はそれぞれ独立に、脂肪族基または芳香族基であり、好ましくはメチル基、エチル基などの脂肪族基を表し、Ｒ_１５は炭素数１〜５のアルキレン基を表す。）The group having a bisphenylene skeleton bonded to the alkylene group in R ₂ may have a substituent and may form a condensed ring. The group having a bisphenylene skeleton bonded with the alkylene group is preferably represented by the following general formula (2-3).

(In formula (2-3), n3 and n4 each independently represent an integer of 0 to 4, and R ₁₃ and R ₁₄ each independently represent an aliphatic group or an aromatic group, preferably a methyl group or ethyl. Represents an aliphatic group such as a group, and R ₁₅ represents an alkylene group having 1 to 5 carbon atoms.)

The alkylene group for R ₁₅ in formula (2-3) may have a substituent such as an aliphatic group or an aromatic group.

The alkylene group for R ₂ is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 to 8 carbon atoms. The alkylene group for R ₂ may have a substituent such as an aliphatic group or an aromatic group.

Since R ₂ is excellent in resolution, it is preferably a group having an alicyclic skeleton, and more preferably a group having an alicyclic skeleton and not an aromatic skeleton.

In the present invention, R ₃ and R _{4 in} formula (1) are each independently a monovalent organic group or a functional group having silicon. Examples of the monovalent organic group for R ₃ and R ₄ include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Examples of the monovalent silicon-containing functional group in R ₃ and R ₄ include a siloxane group, a silane group, and a silanol group.

R ₃ and R ₄ in the formula (1) are preferably alkyl groups from the viewpoint of solubility during synthesis of the polyamic acid ester. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group. Here, the alkyl group is preferably a butyl group, a pentyl group, or a hexyl group.

In the present invention, X in the formula (1) is a divalent organic group, for example, at least a part of an aromatic or aliphatic ester group, an amide group, an amidoimide group, a siloxane group, an epoxy group, an oxetanyl group or the like. The group included as the structure of can be mentioned.

As the polyamic acid ester (A), one type may be used alone, or two or more types may be used in combination. Further, it may be a copolymer in which at least one of R ₁ and R ₂ has a plurality of structures.

The compounding amount of the (A) polyamic acid ester may be, for example, in the range of 5 to 30% by mass based on the total amount of the composition, depending on the coating film thickness and the viscosity.

The (A) polyamic acid ester can be synthesized by a conventionally known method. For example, an acid anhydride such as 3,3′-benzophenonetetracarboxylic acid dianhydride and an alcohol such as ethanol are reacted to form a half ester. The half ester is made into the diester diacid chloride with thionyl chloride. By reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid, the (A) polyamic acid ester can be obtained.

Further, the half ester obtained by reacting the above acid anhydride with alcohol may be reacted with a diisocyanate such as isophorone diisocyanate to obtain (A) polyamic acid ester. Incidentally, the synthetic method using diisocyanate can synthesize the (A) polyamic acid ester more easily than the synthetic method using the above diamine.

The acid anhydride that can be used in the synthesis of the (A) polyamic acid ester is preferably a carboxylic acid dianhydride, and more preferably a tetracarboxylic acid dianhydride. Examples include those represented by the following general formula (3).

（式中のＲ_１は、式（１）で述べたとおりである。）

(R ₁ in the formula is as described in formula (1).)

By using the acid anhydride of the general formula (3) as a raw material for the synthesis of the (A) polyamic acid ester, the R ₁ group in the repeating unit in the polyamic acid ester of the general formula (1) can be easily introduced. it can.

Specific examples of the acid dianhydride applicable to the synthesis of the above (A) polyamic acid ester include ethylene tetracarboxylic acid dianhydride, butane tetracarboxylic acid dianhydride, cyclobutane tetracarboxylic acid dianhydride, and methyl. Aliphatic tetracarboxylic dianhydrides such as cyclobutane tetracarboxylic dianhydride and cyclopentane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride Substance, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3',3,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyltetra Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3',3,4'-biphenyltetracarboxylic dianhydride, 2,2',6,6 '-Biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, bis( 3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2 ,3-Dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3 3,3-hexafluoropropane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-bis [(3,4-Dicarboxy)benzoyl]benzene dianhydride, 1,4-bis[(3,4-dicarboxy)benzoyl]benzene dianhydride, 2,2-bis{4-[4-(1 ,2-Dicarboxy)phenoxy]phenyl}propane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}propane dianhydride, bis{4-[4- (1,2-Dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, 4,4′-bis[4- (1,2-Dicarboxy)phenoxy]biphenyl dianhydride, 4,4′-bis[3-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, bis{4-[4-(1,2 -Dicarboxy)pheno Xy]phenyl}ketone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}ketone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy] Phenyl} sulfone dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl} sulfone dianhydride, bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl} Sulfide dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl} sulfide dianhydride, 2,2-bis{4-[4-(1,2-dicarboxy)phenoxy] Phenyl}-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1, 1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 1,2,3,4-benzenetetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride , 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride, m- Aromatic tetracarboxylic dianhydrides such as terphenyl-3,3',4,4'-tetracarboxylic dianhydride and p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione and the like.

Among the above-mentioned acid dianhydrides, pyromellitic dianhydride, 3,3′,4,4′-benzophenone tetracarboxylic dianhydride, 3,3′,4,4′ as tetracarboxylic dianhydride -Biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis(3,2 4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, 1,3,3a,4 5,9b-Hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1,3-dione is preferred.

Further, R ₁ in the formula (3) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, or a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group. In the acid dianhydride which is a group, the cycloaliphatic skeleton is preferably a cyclohexane skeleton. The acid anhydride preferably has no alkyl group (for example, t-butyl group) on the aromatic skeleton.

The acid anhydride preferably has an acid anhydride group having a succinic anhydride structure. Examples of the acid anhydride group having a succinic anhydride structure include the following acid anhydride groups.

Among the acid anhydrides, the following compounds are preferable.

The molecular weight of the acid anhydride is preferably 600 or less, more preferably 500 or less, still more preferably 400 or less. The lower limit of the molecular weight is preferably 250 or more.

In the synthesis of the (A) polyamic acid ester, one type of acid anhydride may be used alone, or two or more types may be used in combination.

When fluorine-introduced acid dianhydride or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride used in combination, the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. In addition, rigid acid dianhydrides such as pyromellitic dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride are used. When it is used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to impede the improvement of transparency, so that it may be used in combination while paying attention to the copolymerization ratio.

Examples of the diamine that can be used to obtain the (A) polyamic acid ester include diamines represented by the following general formula (4). However, the following are examples, and known ones can be used as long as they do not violate the gist of the present invention.

（式中、Ｒ_２は、式（１）で述べたとおりである。）

(In the formula, R ₂ is as described in the formula (1).)

Examples of the diamine include diaminoisophorone (3-aminomethyl-3,5,5-trimethylcyclohexylamine), toluenediamine, 4,4'-methylenediphenyldiamine, and hexamethylenediamine.

Examples of the diisocyanate that can be used to obtain the (A) polyamic acid ester include diisocyanates represented by the following general formula (5). However, the following are examples, and known ones can be used as long as they do not violate the gist of the present invention.

（式中、Ｒ_２は、式（１）で述べたとおりである。）

(In the formula, R ₂ is as described in the formula (1).)

Examples of the diisocyanate include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), methylenediphenyl 4,4′-diisocyanate (MDI), 2,2-bis(4-isocyanatophenyl)hexafluoropropane, hexamethylene diisocyanate. (HMDI) and the like.

[(B) Photobase generator]
(B) The photobase generator comprises one or more kinds of photobase generators capable of functioning as a catalyst for a ring-closing reaction of a polyamic acid ester when the molecular structure is changed or the molecule is cleaved by irradiation with light such as ultraviolet rays or visible light. A compound that produces a basic substance. The photobase generator (B) may be an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator has a higher composition sensitivity and an excellent resolution. It is preferable because it is advantageous for forming a pattern film. Examples of the basic substance include secondary amines and tertiary amines.

(Nonionic photobase generator)
Examples of the nonionic (B) photobase generator include, for example, α-aminoacetophenone compounds, oxime ester compounds, N-formylated aromatic amino groups, N-acylated aromatic amino groups, nitrobenzylcarbamate groups, and alcohols. Examples thereof include compounds having a substituent such as an oxybenzyl carbamate group.

Other photobase generators include WPBG-018 (Product name: 9-anthrylmethylN,N'-diethylcarbamate), WPBG-027 (Product name: (E)-1-[3-(2-hydroxyphenyl)-2-propenoyl ]piperidine), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate), WPBG-165 and the like can also be used.

The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when it is irradiated with light, it is cleaved in the molecule to generate a basic substance (amine) that exerts a curing catalyst action. Specific examples of the α-aminoacetophenone compound include (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan Ltd.) and 4-(methylthiobenzoyl)-1-methyl. -1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan Ltd.), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]- A commercially available compound such as 1-butanone (Irgacure 379, trade name, manufactured by BASF Japan Ltd.) or a solution thereof can be used.

（式中、Ｒ^１６は、水素原子、無置換または炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されたフェニル基、無置換または１個以上の水酸基で置換された炭素数１〜２０のアルキル基、１個以上の酸素原子で中断された該アルキル基、無置換または炭素数１〜６のアルキル基もしくはフェニル基で置換された炭素数５〜８のシクロアルキル基、無置換または炭素数１〜６のアルキル基もしくはフェニル基で置換された炭素数２〜２０のアルカノイル基またはベンゾイル基を表し、
Ｒ^１７は、無置換または炭素数１〜６のアルキル基、フェニル基もしくはハロゲン原子で置換されたフェニル基、無置換または１個以上の水酸基で置換された炭素数１〜２０のアルキル基、１個以上の酸素原子で中断された該アルキル基、無置換または炭素数１〜６のアルキル基もしくはフェニル基で置換された炭素数５〜８のシクロアルキル基、無置換または炭素数１〜６のアルキル基もしくはフェニル基で置換された炭素数２〜２０のアルカノイル基またはベンゾイル基を表す。）As the oxime ester compound, any compound can be used as long as it is a compound that produces a basic substance upon irradiation with light. As such an oxime ester compound, those having a group represented by the following general formula (6) are preferable.

(In the formula, R ¹⁶ represents a hydrogen atom, an unsubstituted or an alkyl group having 1 to 6 carbon atoms, a phenyl group or a phenyl group substituted with a halogen atom, an unsubstituted or 1 or more hydroxyl group-containing carbon atom 1 -20 alkyl group, the alkyl group interrupted by one or more oxygen atoms, unsubstituted or C5-C6 cycloalkyl group substituted by a C1-C6 alkyl group or phenyl group, unsubstituted Or represents an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group,
R ¹⁷ is an unsubstituted or C 1-6 alkyl group, a phenyl group or a phenyl group substituted with a halogen atom, an unsubstituted or a C 1-20 alkyl group substituted with one or more hydroxyl groups, 1 The alkyl group interrupted with one or more oxygen atoms, an unsubstituted or an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms substituted with a phenyl group, unsubstituted or having 1 to 6 carbon atoms It represents an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group substituted with an alkyl group or a phenyl group. )

（式中、Ｒ^１８およびＲ^１９は、それぞれ独立に水素または１価の有機基であり、それらは同一であっても異なっていてもよい。また、それら２つが結合して環状構造を形成していてもよい。）Further, the oxime ester compound may have a group represented by the following formula (7).

(In the formula, R ¹⁸ and R ¹⁹ are each independently hydrogen or a monovalent organic group, and they may be the same or different. Further, these two are bonded to each other to form a cyclic structure. May be.)

Examples of commercially available oxime ester-based photobase generators include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan Ltd., N-1919 and NCI-831 produced by Adeka. Further, the compound having two oxime ester groups in the molecule described in Japanese Patent No. 4344400 can also be preferably used.

In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, and JP-A-2008-509967, Examples include carbazole oxime ester compounds described in JP-A-2009-040762 and JP-A-2011-80036.

As the photobase generator (B), a photobase generator having a carbamate structure represented by the following general formula (8) and a photobase generator represented by the following general formulas (9) and (10) may be used. ..

（式中、Ｒ^２０、Ｒ^２１、Ｒ^２２及びＲ^２３は、それぞれ独立して水素、置換基を有していてもよい炭素数１〜６のアルキル基、置換基を有していてもよい炭素数３〜８のシクロアルキル基、置換基を有していてもよい炭素数１〜６のアルコキシル基、置換基を有していてもよい炭素数１〜６のアルケン基、置換基を有していてもよい炭素数１〜６のアルキニル基、置換基を有していてもよいアリール基、または置換基を有していてもよい複素環基を示し（ただし、Ｒ^２０、Ｒ^２１、Ｒ^２２およびＲ^２３のうちの少なくとも一つは水素ではない）、Ｒ^２４およびＲ^２５は、それぞれ独立して水素、置換基を有していてもよい炭素数１〜６のアルキル基、置換基を有していてもよい炭素数３〜８シクロアルキル基、置換基を有していてもよい炭素数１〜６のアルコキシル基、置換基を有していてもよい炭素数１〜６のアルケン基、置換基を有していてもよい炭素数１〜６のアルキニル基、置換基を有していてもよいアリール基、置換基を有していてもよい複素環基、互いに結合して形成される置換基を有していてもよい単環、または互いに結合して形成される置換基を有していてもよい多環を示し、式中、Ｒ^２６は置換基を有していてもよいニトロフェニル基を示し、Ｒ^２７およびＲ^２８は、それぞれ独立して水素、または置換基を有していてもよい炭素数１〜６のアルキル基を示す。）

(In the formula, R ²⁰ , R ²¹ , R ²² and R ²³ each independently have hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent or a substituent. A cycloalkyl group having 3 to 8 carbon atoms, an alkoxyl group having 1 to 6 carbon atoms which may have a substituent, an alkene group having 1 to 6 carbon atoms which may have a substituent, and a substituent Represents an optionally substituted alkynyl group having 1 to 6 carbon atoms, an aryl group optionally having a substituent, or a heterocyclic group optionally having a substituent (provided that R ²⁰ , R ²¹ , At least one of R ²² and R ²³ is not hydrogen), R ²⁴ and R ²⁵ are each independently hydrogen, an optionally substituted alkyl group having 1 to 6 carbon atoms, or a substituent. A cycloalkyl group having 3 to 8 carbon atoms which may have, an alkoxyl group having 1 to 6 carbon atoms which may have a substituent, and an alkene having 1 to 6 carbon atoms which may have a substituent. Group, optionally substituted alkynyl group having 1 to 6 carbon atoms, optionally substituted aryl group, optionally substituted heterocyclic group, formed by bonding to each other Represents a monocyclic ring which may have a substituent or a polycyclic ring which may be formed by bonding with each other, and in the formula, R ²⁶ may have a substituent. A preferable nitrophenyl group, and R ²⁷ and R ²⁸ each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms which may have a substituent.)

（式中、Ｒ^２９およびＲ^３０は、それぞれ独立に、水素または１価の有機基であり、同一であっても異なっていてもよい。Ｒ^２９およびＲ^３０は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。但し、Ｒ^２９およびＲ^３０の少なくとも１つは１価の有機基である。Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それぞれ独立に、水素、ハロゲン、水酸基、ニトロ基、ニトロソ基、メルカプト基、シリル基、シラノール基または１価の有機基であり、同一であっても異なっていてもよい。Ｒ^３１、Ｒ^３２、Ｒ^３３およびＲ^３４は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。）

(In the formula, R ²⁹ and R ³⁰ are each independently hydrogen or a monovalent organic group, and may be the same or different. R ²⁹ and R ³⁰ are bonded to each other to form a cyclic structure. And may contain a bond of a heteroatom, provided that at least one of R ²⁹ and R ³⁰ is a monovalent organic group, R ³¹ , R ³² , R ³³ and R ^34. are each independently hydrogen, halogen, hydroxyl, nitro, nitroso group, a mercapto group, a silyl group, a silanol group or a monovalent organic group, it may be different even in the same .R ^31, R Two or more of ³² , R ³³ and R ³⁴ may be bonded to each other to form a cyclic structure, and may include a bond of a hetero atom.)

（式（１０）中、Ｒ^３５は、非置換であるか、または、１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、ＮＲ^４２Ｒ^４３、ＣＮ、ＯＲ^４４、ＳＲ^４５、ＣＯＲ^４６、ＣＯＯＲ^４７、ハロゲンまたは式（１１）

によって置換された芳香族または複素芳香族基であり；あるいは
Ｒ^３５は、式（１２）

によって表わされる基であり；
Ｒ^３６およびＲ^３７は、互いに独立して、水素、アルキル、アルケニル、アルキニルであるか、非置換または１つ以上のアルキル、ＣＮ、ＯＲ^４４、ＳＲ^４５、ハロゲンまたはハロアルキルによって置換されたフェニルであり；
Ｒ^３９は、アルキルまたはＮＲ^４４ＡＲ^４５Ａであり；Ｒ^４４ＡおよびＲ^４５Ａは、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；
Ｒ^３８、Ｒ^４０、Ｒ^４１、Ｒ^４２およびＲ^４３は、互いに独立して、水素またはアルキルであり；あるいは
Ｒ^３８およびＲ^４０は、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；あるいは
Ｒ^３９およびＲ^４１は、Ｒ^３８およびＲ^４０から独立して、ともに、非置換であるか、または１つ以上のアルキルによって置換されたアルキレンブリッジを形成し；
Ｒ^４４、Ｒ^４５およびＲ^４７は、互いに独立して、水素またはアルキルであり；
Ｒ^４６は水素またはアルキルであり；あるいは、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、ＮＲ^４２Ｒ^４３、ＣＮ、ＯＲ^４４、ＳＲ^４５、ＣＯＲ^４４、ＣＯＯＲ^４７、またはハロゲンによって置換された芳香族または複素芳香族基であり；
Ｒ^４８は、非置換であるか、または１つ以上のアルキル、アルケニル、アルキニル、ハロアルキル、ＮＲ^４２Ｒ^４３、ＣＮ、ＯＲ^４４、ＳＲ^４５、ＣＯＲ^４６、ＣＯＯＲ^４７、またはハロゲンによって置換された芳香族または複素芳香族基であり；
Ｒ^４９は、水素またはアルキルであり；
Ｒ^５０は、水素、アルキル、あるいは非置換であるか、または１つ以上のアルキル、ビニル、アルケニル、アルキニル、ハロアルキル、フェニル、ＮＲ^４２Ｒ^４３、ＣＮ、ＯＲ^４４、ＳＲ^４５、ＣＯＲ^４６、ＣＯＯＲ^４７またはハロゲンによって置換されたフェニルである。）

(In formula (10), R ³⁵ is unsubstituted or one or more of alkyl, alkenyl, alkynyl, haloalkyl, NR ⁴² R ⁴³ , CN, OR ⁴⁴ , SR ⁴⁵ , COR ⁴⁶ , COOR ⁴⁷ , Halogen or formula (11)

An aromatic or heteroaromatic group substituted by; or R ³⁵ is of the formula (12)

Is a group represented by;
R ³⁶ and R ³⁷ are, independently of one another, hydrogen, alkyl, alkenyl, alkynyl, or phenyl, unsubstituted or substituted by one or more alkyl, CN, OR ⁴⁴ , SR ⁴⁵ , halogen or haloalkyl. ;
R ³⁹ is alkyl or NR ^44A R ^45A ; R ^44A and R ^45A together form an alkylene bridge which is unsubstituted or substituted by one or more alkyls;
R ³⁸ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ , independently of each other, are hydrogen or alkyl; or R ³⁸ and R ⁴⁰ are both unsubstituted or by one or more alkyl Or R ³⁹ and R ⁴¹ , independently of R ³⁸ and R ⁴⁰ , together form an alkylene bridge which is unsubstituted or substituted by one or more alkyls. ;
R ⁴⁴ , R ⁴⁵ and R ⁴⁷ , independently of each other, are hydrogen or alkyl;
R ⁴⁶ is hydrogen or alkyl; or is unsubstituted or is one or more of alkyl, alkenyl, alkynyl, haloalkyl, NR ⁴² R ⁴³ , CN, OR ⁴⁴ , SR ⁴⁵ , COR ⁴⁴ , COOR ⁴⁷ , or An aromatic or heteroaromatic group substituted by halogen;
R ⁴⁸ is unsubstituted or aromatic substituted with one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ⁴² R ⁴³ , CN, OR ⁴⁴ , SR ⁴⁵ , COR ⁴⁶ , COOR ⁴⁷ , or halogen. Or a heteroaromatic group;
R ⁴⁹ is hydrogen or alkyl;
R ⁵⁰ is hydrogen, alkyl, or unsubstituted or one or more of alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR ⁴² R ⁴³ , CN, OR ⁴⁴ , SR ⁴⁵ , COR ⁴⁶ , COOR ^47. Or phenyl substituted by halogen. )

(Ionic photobase generator)
Examples of the ionic (B) photobase generator include salts of aromatic component-containing carboxylic acids represented by the following general formula (13) with tertiary amines, the following general formulas (14) to (18), The photobase generator represented by (23) and (24), WPBG-082, WPBG-167, WPBG-168, WPBG-266, WPBG- of Wako Pure Chemical Industries, Ltd. ion type PBG represented by the following structural formula. 300 or the like can be used.

（式中、Ｒ^５１〜Ｒ^６０は、それぞれ独立に、水素または１価の有機基である。）

(In the formula, R ^{51 to} R ⁶⁰ are each independently hydrogen or a monovalent organic group.)

（式（１４）中、Ａｒは、下記一般式［Ｉ］で示されるクマリニル基、および下記一般式［ＩＩ］で示されるアセナフテニル基からなる群より選ばれる何れかの基を表し、Ｙ^＋は、下記一般式［ＩＩＩ］で示される基、下記一般式［ＩＶ］で示される基、下記式［Ｖ］で示される基、下記式［ＶＩ］で示される基、および下記一般式［ＶＩＩ］で示される基からなる群より選ばれる何れかの基を表し、Ｚ⁻は、ハロゲンアニオン、ボレートアニオン、Ｎ，Ｎ−ジメチルカルバメートアニオン、Ｎ，Ｎ−ジメチルジチオカルバメートアニオン、チオシアネートアニオン、シアネートアニオン、安息香酸アニオン、またはベンゾイルぎ酸アニオンを表し、Ｒ^６１およびＲ^６２はそれぞれ独立して、水素原子、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基または置換基を有していてもよいフェニル基を表す。）

（式［Ｉ］および式［ＩＩ］中、ｍ個のＲ^６３およびｎ個のＲ^６４はそれぞれ独立して、ハロゲン原子、炭素数２〜１０の直鎖状、分枝状若しくは環状のアルキルカルボニル基または炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基を表す。ｍは、０〜５の整数を表し、ｎは、０〜７の整数を表す。）

（式［ＩＩＩ］中、Ｒ^６５〜Ｒ^６７はそれぞれ独立して、炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基を表す。式［ＩＶ］中、Ａは、窒素原子またはメチン基（ＣＨ基）を表し、Ｒ^６８は、水素原子またはヒドロキシル基を表す。一般式［ＶＩＩ］中、Ｒ^６９およびＲ^７０はそれぞれ独立して、水素原子または炭素数１〜１０の直鎖状、分枝状若しくは環状のアルキル基を表す。）

(In the formula (14), Ar represents any group selected from the group consisting of a coumarinyl group represented by the following general formula [I] and an acenaphthenyl group represented by the following general formula [II], and Y ⁺ is A group represented by the following general formula [III], a group represented by the following general formula [IV], a group represented by the following formula [V], a group represented by the following formula [VI], and a general formula [VII] Represents any group selected from the group consisting of groups, Z ⁻ represents a halogen anion, borate anion, N,N-dimethylcarbamate anion, N,N-dimethyldithiocarbamate anion, thiocyanate anion, cyanate anion, Represents a benzoate anion or benzoylformate anion, and R ⁶¹ and R ⁶² each independently have a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a substituent. Represents a phenyl group which may be present.)

(In the formula [I] and the formula [II], m R ⁶³ and n R ⁶⁴ are each independently a halogen atom, a linear, branched or cyclic alkylcarbonyl having 2 to 10 carbon atoms. Represents a group or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, m represents an integer of 0 to 5, and n represents an integer of 0 to 7.)

(In the formula [III], R ^{65 to} R ⁶⁷ each independently represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. In the formula [IV], A is a nitrogen atom. Or a methine group (CH group), R ⁶⁸ represents a hydrogen atom or a hydroxyl group, and in the general formula [VII], R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom or a straight chain having 1 to 10 carbon atoms. Represents a chain, branched or cyclic alkyl group.)

（式（１５）および式（１６）中、Ｒ^７１、Ｒ^７２およびＲ^７３は、それぞれ独立に、水素原子または有機基であり、同一であっても異なっていてもよい。Ｒ^７１、Ｒ^７２およびＲ^７３は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。但し、Ｒ^７１、Ｒ^７２およびＲ^７３の少なくとも１つは有機基である。Ｒ^７４、Ｒ^７６およびＲ^７７はそれぞれ独立に、水素原子または有機基であり、同一であっても異なっていてもよい。Ｒ^７５は水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基または有機基である。Ｒ^７４、Ｒ^７５、Ｒ^７６およびＲ^７７は、それらが結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^７８およびＲ^７９はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、または有機基であり、同一であっても異なっていてもよい。Ｒ^８０、Ｒ^８１、Ｒ^８２およびＲ^８３は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基または有機基であり、同一であっても異なっていてもよい。Ｒ^８０、Ｒ^８１、Ｒ^８２およびＲ^８３は、それらの２つ以上が結合して環状構造を形成していてもよく、ヘテロ原子の結合を含んでいてもよい。Ｒ^８４は、水素原子、或いは、加熱および電磁波の照射の少なくとも何れか一方により脱保護可能な保護基である。）

(In Formula (15) and Formula (16), R ⁷¹ , R ^72, and R ⁷³ each independently represent a hydrogen atom or an organic group, and may be the same or different. R ⁷¹ , R ⁷² And R ⁷³ may combine with each other to form a cyclic structure, and may contain a bond of a hetero atom, provided that at least one of R ⁷¹ , R ⁷² and R ⁷³ is an organic group. R ⁷⁴ , R ⁷⁶ and R ⁷⁷ each independently represent a hydrogen atom or an organic group, which may be the same or different, R ⁷⁵ represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, silyl group, a silanol group, a nitro group, a nitroso group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, an ammonio group or an organic group ^{.R 74, R 75,} R ⁷⁶ and ^{R 77} are, they R ⁷⁸ and R ⁷⁹ may each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group or a silyl group. , silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group or an organic group, may .R ⁸⁰ be different even in the same, , R ⁸¹ , R ⁸² and R ⁸³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonato group, A phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group or an organic group, which may be the same or different, and R ⁸⁰ , R ⁸¹ , R ⁸² and R ⁸³ are the same as those 2 One or more may be bonded to each other to form a cyclic structure, and may include a bond of a hetero atom, R ⁸⁴ is a hydrogen atom, or deprotectable by at least one of heating and irradiation with electromagnetic waves. It is a protective group.)

（式（１７）および式（１８）中、Ｒ^８５およびＲ^８６は、炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基、炭素数２〜１８のアルキニル基、炭素数６〜１４のアリール基、ニトロ基、水酸基、シアノ基、ＯＲ^８７で表されるアルコキシ基、ＮＲ^８８Ｒ^８９で表されるアミノ基、Ｒ^９０ＣＯで表されるアシル基、Ｒ^９１ＣＯＯで表されるアシロキシ基、ＳＲ^９２で表されるアルキルチオ基若しくはアリールチオ基、またはハロゲン原子であり、Ｒ^８７、Ｒ^９０、Ｒ^９１およびＲ^９２は炭素数１〜８のアルキル基または炭素数６〜１２のアリール基、Ｒ^８８およびＲ^８９は水素原子、炭素数１〜８のアルキル基または炭素数６〜１２のアリール基、ｎは０〜７の整数、ｍは０〜９の整数である。Ｙ^＋は下記式（１９）〜（２２）の何れかで表される第４級アンモニオ基であり、Ｑは窒素原子またはメチン基（ＣＨ）、ｔおよびｕは２または３、ｗは０〜２の整数、Ａは水素原子、水酸基またはハロゲン原子、Ｒ^９３〜Ｒ^９５は炭素数１〜１８のアルキル基、炭素数２〜１８のアルケニル基または炭素数６〜１４のアリール基である。Ｒ^８５またはＲ^８６とＣＨ_２−Ｙ^＋Ｘ⁻とは同じベンゼン環に結合していてもよいし、異なったベンゼン環に結合していてもよい。Ｘ⁻はボレートアニオン、フェノラートアニオンおよびカルボキシレートアニオンから選ばれるカウンターアニオンである。）

(In formula (17) and formula (18), R ⁸⁵ and R ⁸⁶ are each an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, and 6 to 6 carbon atoms. 14 aryl group, nitro group, hydroxyl group, cyano group, alkoxy group represented by OR ⁸⁷ , amino group represented by NR ⁸⁸ R ⁸⁹ , acyl group represented by R ⁹⁰ CO, and represented by R ⁹¹ COO An acyloxy group, an alkylthio group or an arylthio group represented by SR ⁹² , or a halogen atom, and R ^87, R ⁹⁰ , R ⁹¹ and R ⁹² are an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms , R ⁸⁸ and R ⁸⁹ are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms, n is an integer of 0 to 7 and m is an integer of 0 to 9. Y ⁺ is as follows. A quaternary ammonio group represented by any of formulas (19) to (22), Q is a nitrogen atom or a methine group (CH), t and u are 2 or 3, w is an integer of 0 to 2, A is a hydrogen atom, a hydroxyl group or a halogen atom, and R ^{93 to} R ⁹⁵ are an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or an aryl group having 6 to 14 carbon atoms R ⁸⁵ or R ^86. And CH ₂ —Y ⁺ X ⁻ may be bonded to the same benzene ring or different benzene rings, and X ⁻ is selected from borate anion, phenolate anion and carboxylate anion. It is a counter anion.)

（式（２３）中、Ｘ^１、Ｘ^２は独立に酸素原子もしくは硫黄原子を示す。Ｒ^９６〜Ｒ^１０４は独立に水素原子、ハロゲン原子、ヒドロキシル基、メルカプト基、ニトロ基、シリル基、シラノール基、もしくは１価の有機基を示す。Ｒ^１０５、Ｒ^１０６、Ｒ^１０７は水素原子、もしくは１価の有機基を示す。但し、Ｒ^１０５、Ｒ^１０６、Ｒ^１０７の少なくとも１つは、１価の有機基である。）

(In the formula (23), X ¹ and X ² independently represent an oxygen atom or a sulfur atom. R ^{96 to} R ¹⁰⁴ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, and a silanol. Group, or a monovalent organic group, R ¹⁰⁵ , R ¹⁰⁶ , and R ¹⁰⁷ represent a hydrogen atom or a monovalent organic group, provided that at least one of R ¹⁰⁵ , R ¹⁰⁶ , and R ¹⁰⁷ is a monovalent group. Is an organic group.)

（式（２４）中、Ｒ^１０８〜Ｒ^１１７は、それぞれ独立に水素または１価の有機基であり、それらの２つ以上が同一であっても全てが異なってもいてもよい。また、それらの２つ以上が結合して環状構造を形成していてもよい。Ｒ^１１８〜Ｒ^１２０は、それぞれ独立に水素または１価の有機基であり、それらの２つ以上が同一であっても異なってもいてもよい。また、それらの２つ以上が結合して環状構造を形成していてもよい。Ｒ^１２１は、水素または１価の有機基である。Ａは、陰イオンとなりえる化合物または元素である。）

(In formula (24), R ^{108 to} R ¹¹⁷ are each independently hydrogen or a monovalent organic group, and two or more thereof may be the same or all may be different. May be bonded to each other to form a cyclic structure, and R ^{118 to} R ¹²⁰ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or different. Two or more of them may be bonded to each other to form a cyclic structure, R ¹²¹ is hydrogen or a monovalent organic group, and A is a compound capable of being an anion or It is an element.)

Ion type PBGs such as WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG-300 manufactured by Wako Pure Chemical Industries, which are represented by the following structural formulas can be used.

WPBG-082

WPBG-167

WPBG-168

WPBG-266

WPBG-300

As the photobase generator (B), one type may be used alone, or two or more types may be used in combination. The compounding amount of the photobase generator (B) is preferably 5 to 50% by mass based on the total amount of the composition. When it is 5 to 50% by mass, the resolution is more excellent.

When the coating film of the photosensitive resin composition is irradiated with actinic rays, (A) the polyamic acid ester and (B) the photobase generator so that the decomposition of the (B) photobase generator proceeds uniformly in the thickness direction. The combination and the addition amount of are appropriately selected according to the coating film thickness and the like. It is preferable to use the (A) polyamic acid ester having small absorption with respect to the wavelength of the actinic ray so that the exposure amount can be reduced and the film can be made thicker. The absorption characteristics can be appropriately changed by the molecular design of the (A) polyamic acid ester. For example, in order to shift the absorption region to a short wavelength, (A) a polyamic acid ester having an aromatic group is used, and the conjugated system such as R ₁ and/or R ₂ is shortened, or the charge transfer complex It is useful to prevent formation.

The other components that can be incorporated into the photosensitive resin composition of the present invention are described below.

The solvent that can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it can dissolve (A) a polyamic acid ester, (B) a photobase generator, and other additives. As an example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ- Examples thereof include butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ-butyrolactone and diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. Although the amount of the solvent used is not particularly limited, for example, it may be used in the range of 50 to 9000 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester, depending on the coating film thickness and the viscosity.

A sensitizer may be added to the photosensitive resin composition of the present invention in order to further improve photosensitivity. Examples of the sensitizer include Michler's ketone, 4,4′-bis(diethylamino)benzophenone, 2,5-bis(4′-diethylaminobenzal)cyclopentane, 2,6-bis(4′-diethylaminobenzal)cyclohexanone. 2,6-bis(4′-dimethylaminobenzal)-4-methylcyclohexanone, 2,6-bis(4′-diethylaminobenzal)-4-methylcyclohexanone, 4,4′-bis(dimethylamino) Chalcone, 4,4′-bis(diethylamino) chalcone, p-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p- Dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4′-dimethylaminobenzal)acetone, 1,3-bis(4′-diethylaminobenzal) ) Acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin , 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N′-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2 -(P-Dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene and the like are mentioned, and in terms of sensitivity, It is preferable to use thioxanthones such as 4-(1-methylethyl)-9H-thioxanthen-9-one. These can be used alone or in combination of 2 to 5 types. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester.

Further, the photosensitive resin composition of the present invention may contain an adhesion aid for improving the adhesiveness to the substrate. As the adhesion aid, known ones can be used as long as they do not violate the gist of the present invention. For example, γ-aminopropyldimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, N-[3-( Examples thereof include reaction products of (triethoxysilyl)propyl]phthalamic acid, benzophenonetetracarboxylic dianhydride and (triethoxysilyl)propylamine. The compounding amount of the adhesion aid is preferably in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamic acid ester.

Moreover, you may add a base multiplying agent to the photosensitive resin composition of this invention. When forming a thick film pattern, the same degree of decomposition of the photobase generator (B) from the surface to the bottom is required. In this case, it is preferable to add a base multiplying agent in order to improve the sensitivity. For example, it is possible to use the base multiplying agents disclosed in JP2012-237776A, JP2006-282657A and the like.

It should be noted that the photosensitive resin composition of the present invention may contain other photosensitive components that generate an acid by light, as long as the film characteristics after curing are not significantly impaired. When adding a compound having one or two or more ethylenically unsaturated bonds to the photosensitive resin composition of the present invention, a photoradical generator may be added.

In addition, various organic or inorganic low-molecular or high-molecular compounds may be added to the photosensitive resin composition of the present invention in order to impart processing characteristics and various functionalities. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, which may have a porous or hollow structure. Specific materials for obtaining a porous shape and a hollow structure include various pigments, fillers, fibers and the like.

The dry film of the present invention has a resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film (support). The formation of a dry film is carried out by diluting the photosensitive resin composition of the present invention with the above organic solvent to an appropriate viscosity, and then using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer coater. Apply to a uniform thickness on the carrier film with a roll coater, gravure coater, spray coater, or the like. Then, the applied photosensitive resin composition is usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected within the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film is used, and it is preferable to use a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film or the like plastic film. The thickness of the carrier film is not particularly limited, but generally, it is appropriately selected within the range of 10 to 150 μm.

After forming a resin layer comprising the photosensitive resin composition of the present invention on the carrier film, for the purpose of preventing dust from adhering to the surface of the film, a peelable cover film is further provided on the surface of the film. It is preferable to stack them. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. Any cover film may be used as long as it has a smaller adhesive force between the resin layer and the carrier film when the cover film is peeled off.

Next, a method for producing a patterned film as a cured product using the photosensitive resin composition of the present invention will be described.

First, in step 1, the photosensitive resin composition is applied onto a substrate and dried to obtain a coating film. The method for applying the photosensitive resin composition onto the substrate is a method that has been conventionally used for applying the photosensitive resin composition, for example, a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like. Can be used, a spray coating method using a spray coater, and an inkjet method can be used. As a method for drying the coating film, air drying, heat drying using an oven or a hot plate, vacuum drying and the like are used. Further, it is desirable that the coating film is dried under the condition that the imidization of the (A) polyamic acid ester in the photosensitive resin composition does not occur. Specifically, natural drying, blast drying, or heat drying can be performed at 20 to 140° C. for 1 minute to 1 hour. Preferably, it is dried on a hot plate for 1 to 20 minutes. Vacuum drying is also possible, and in this case, it can be performed at room temperature for 1 minute to 1 hour.

The base material is not particularly limited, and can be widely applied to silicon wafers, wiring boards, various resins, metals, passivation protective films for semiconductor devices, and the like.

Further, since it can be imidized at a low temperature, it can be widely applied to members and materials which are not suitable for high temperature treatment such as a substrate of a printed wiring board.

Next, in step 2, the coating film is exposed through a photomask having a pattern or directly. The exposure light has a wavelength capable of activating the photobase generator (B) to generate a base. As described above, the photosensitivity can be adjusted by using an appropriate sensitizer. As the exposure device, a contact aligner, a mirror projection, a stepper, a laser direct exposure device or the like can be used.

Subsequently, in step 3, heating is performed so as to promote imidization of the coating film by the base generated in the coating film. As a result, the base generated in the exposed portion in step 2 serves as a catalyst to partially imidize the polyamic acid ester (A). The heating time and the heating temperature are appropriately changed depending on the type of the (A) polyamic acid ester used, the coating film thickness, and the (B) photobase generator. Typically, for a coating film thickness of about 10 μm, it is about 2 to 10 minutes at 110 to 200° C. If the heating temperature is too low, partial imidization cannot be efficiently achieved. On the other hand, if the heating temperature is too high, imidization of the unexposed area proceeds, reducing the solubility difference between the exposed area and the unexposed area, which may hinder pattern formation.

Next, in step 4, the coating film is treated with a developing solution. As a result, the pattern film composed of the (A) polyamic acid ester and the partially imidized polyimide can be formed on the substrate.

As a method used for development, any method can be selected from conventionally known photoresist development methods, for example, a rotary spray method, a paddle method, and a dipping method accompanied by ultrasonic treatment. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia water, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide. Examples thereof include aqueous solutions of quaternary ammonium salts and the like. If necessary, a water-soluble organic solvent such as methanol, ethanol or isopropyl alcohol or a surfactant may be added thereto in an appropriate amount to prepare an aqueous solution. Then, if necessary, the coating film is washed with a rinse liquid to obtain a patterned film. As the rinse liquid, distilled water, methanol, ethanol, isopropanol, or the like can be used alone or in combination.
Examples of the developing solution include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and hexamethylphosphortrilide. Amide, methanol, ethanol, isopropyl alcohol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropio An organic solvent such as nate, 2-heptanone, ethyl acetate, diacetone alcohol may be used.

Then, in step 5, the pattern film is heated. The heating temperature is appropriately set so that the polyimide pattern film can be cured. For example, heating is performed at 150 to 300° C. for about 5 to 120 minutes in an inert gas. A more preferable range of the heating temperature is 150 to 250°C, and a still more preferable range is 180 to 220°C. The heating is performed by using, for example, a hot plate, an oven, or a temperature rising type oven in which a temperature program can be set. As the atmosphere (gas) at this time, air may be used, or an inert gas such as nitrogen or argon may be used.

The application of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include printing ink, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, building materials, three-dimensional modeling, optical members, etc. , Publicly known various fields and products in which resin materials are used. In particular, a wide range of fields and products where properties such as heat resistance, dimensional stability, and insulation properties of polyimide films are effective, such as paints or printing inks, or color filters, films for flexible displays, semiconductor devices, electronic parts, It is preferably used as a material for forming an interlayer insulating film, a wiring coating film such as a solder resist, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member or a building material.

In particular, the photosensitive resin composition of the present invention containing (A) polyamic acid ester is mainly used as a pattern forming material (resist), and the pattern film formed thereby is heat resistant as a permanent film made of polyimide. And functions as a component that imparts insulation properties, such as color filters, films for flexible displays, electronic components, semiconductor devices, interlayer insulating films, wiring coating films such as solder resists and coverlay films, solder dams, optical circuits, and light. It is suitable for forming circuit parts, antireflection films, and other optical members or electronic members.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

[Synthesis Example 1: Synthesis of polyamic acid ester A-1]
About 5 g of dry MeOH was added to 5 g of 6FDA (4,4′-(hexafluoroisopropylidene)diphthalic anhydride) as an acid dianhydride, and the mixture was refluxed. About 30 minutes after the start of reflux, an almost transparent liquid was obtained. Further, the mixture was refluxed for about 5 hours, cooled, and filtered through a filter having a pore size of 0.7 μm to remove impurities. After drying under reduced pressure to completely remove MeOH, half-esters of acid anhydrides shown in Table 1 were obtained as white crystals.
Into a three-necked flask having a capacity of 100 ml, 5 mmol of half ester of the acid anhydride described in Table 1 and 0.0125 mmol of anhydrous 3-methyl-1-phenyl-2-phosphorene 1-oxide were charged, and then 10 ml of 10 ml was added while flowing nitrogen. It was dissolved with dehydrated sulfolane. As the diisocyanate, 5 mmol of anhydrous ITI (isophorone diisocyanate) was dissolved in 5 ml of dehydrated sulfolane and added dropwise to the flask in about 5 minutes. The mixed solution was reacted at 200° C. for 3 hours and precipitated with 500 ml of MeOH. The solution containing the precipitate was filtered and dried to obtain a polymer precursor polymer. The obtained polymer was dissolved in DMAc (N,N-dimethylacetamide) and reprecipitated with MeOH. Filtration and drying were performed to prepare a 15% by mass polyamic acid ester A-1 solution using dehydrated DMAc as a solvent.

[Synthesis Example 2: Synthesis of polyamic acid ester A-2]
A polyamic acid ester A-2 solution was prepared in the same manner as in Synthesis Example 1 except that PMDA (pyromellitic anhydride) was used instead of 6FDA as the acid dianhydride.

[Synthesis Example 3: Synthesis of polyamic acid ester A-3]
As the diisocyanate, a polyamic acid ester A-3 solution was prepared in the same manner as in Synthesis Example 1 except that anhydrous ITI was changed to anhydrous MDI (methylenediphenyl 4,4′-diisocyanate) shown in the following table.

[Synthesis Example 4: Synthesis of polyamic acid ester A-4]
A polyamic acid ester A-4 solution was prepared in the same manner as in Synthesis Example 1 except that 6FDA was changed to PMDA as the acid dianhydride and anhydrous ITI was changed to anhydrous MDI shown in the following table as the diisocyanate.

[Synthesis Example 5: Synthesis of polyamic acid ester A-5]
As the diisocyanate, a polyamic acid ester A-5 solution was prepared in the same manner as in Synthesis Example 1 except that the anhydrous TTI was changed to anhydrous TDI-1 (2,4-toluene diisocyanate) shown in the table below.

[Synthesis Example 6: Synthesis of polyamic acid ester A-6]
A polyamic acid ester A-6 solution was prepared in the same manner as in Synthesis Example 1 except that 6FDA was changed to PMDA as the acid dianhydride, and anhydrous ITI was changed to anhydrous TDI-1 shown in the following table as the diisocyanate. did.

[Synthesis Example 7: Synthesis of polyamic acid ester A-7]
As an acid dianhydride, 6FDA was converted into TDA (1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxo-3-furanyl)naphtho[1,2-c]furan-1, 3-dione), as the diisocyanate, except that the anhydrous ITI was changed to a mixture of anhydrous TDI-2 (2,4-toluene diisocyanate and 2,6-toluene diisocyanate (80:20) shown in the following table, A polyamic acid ester A-7 solution was prepared in the same manner as in Synthesis Example 1.

[Synthesis Example 8: Synthesis of polyamic acid ester A-8]
A polyamic acid ester A-8 solution was prepared in the same manner as in Synthesis Example 1 except that 6FDA was changed to TDA as the acid dianhydride, and anhydrous ITI was changed to anhydrous MDI shown in the following table as the diisocyanate.

[Synthesis Example 9: Synthesis of polyamic acid ester A-9]
A polyamic acid ester A-9 solution was prepared in the same manner as in Synthesis Example 1 except that 6FDA was changed to TDA as the acid dianhydride.

[Synthesis Example 10: Synthesis of polyamic acid ester A-10]
As the acid dianhydride, 6FDA was changed to PMDA, and as the diisocyanate, the anhydrous ITI was changed to anhydrous HMDI (hexamethylene diisocyanate) shown in the following table, and polyamic acid ester A-10 was prepared in the same manner as in Synthesis Example 1. A solution was made.

[Synthesis Example 11: Synthesis of polyamic acid ester A-11]
A polyamic acid ester A-11 solution was prepared in the same manner as in Synthesis Example 1 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 1.

[Synthesis Example 12: Synthesis of polyamic acid ester A-12]
A polyamic acid ester A-12 solution was prepared in the same manner as in Synthesis Example 2 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 2.

[Synthesis Example 13: Synthesis of polyamic acid ester A-13]
A polyamic acid ester A-13 solution was prepared in the same manner as in Synthesis Example 3 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 3.

[Synthesis Example 14: Synthesis of polyamic acid ester A-14]
A polyamic acid ester A-14 solution was prepared in the same manner as in Synthesis Example 4, except that MeOH was changed to tert-butyl alcohol in Synthesis Example 4.

[Synthesis Example 15: Synthesis of polyamic acid ester A-15]
A polyamic acid ester A-15 solution was prepared in the same manner as in Synthesis Example 5, except that MeOH was changed to tert-butyl alcohol in Synthesis Example 5.

[Synthesis Example 16: Synthesis of polyamic acid ester A-16]
A polyamic acid ester A-16 solution was prepared in the same manner as in Synthesis Example 6 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 6.

[Synthesis Example 17: Synthesis of polyamic acid ester A-17]
A polyamic acid ester A-17 solution was prepared in the same manner as in Synthesis Example 7, except that MeOH was changed to tert-butyl alcohol in Synthesis Example 7.

[Synthesis Example 18: Synthesis of polyamic acid ester A-18]
A polyamic acid ester A-18 solution was prepared in the same manner as in Synthesis Example 8 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 8.

[Synthesis Example 19: Synthesis of polyamic acid ester A-19]
A polyamic acid ester A-19 solution was prepared in the same manner as in Synthesis Example 9 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 9.

[Synthesis Example 20: Synthesis of polyamic acid ester A-20]
A polyamic acid ester A-20 solution was prepared in the same manner as in Synthesis Example 10 except that MeOH was changed to tert-butyl alcohol in Synthesis Example 10.

[Comparative Synthesis Example 1: Synthesis of polyamic acid R-1]
In a separable flask having a volume of 300 ml, 30 mmol of the diamine shown in the following table was charged, and then the diamine was dissolved with dehydrated DMAc (N,N-dimethylacetamide) while flowing nitrogen. After all the diamines were dissolved, 30 mmol of 6FDA shown in the table below was gradually added as an acid anhydride. 6FDA attached to the wall of the flask was poured into the reaction solution with a small amount of DMAc, and then the mixture was stirred and reacted at room temperature for 24 hours to obtain a 15% by mass polyamic acid solution. The amount of dehydrated DMAc added was 75% by mass of the amount of the solution of polyamic acid.

[Comparative Synthesis Example 2: Synthesis of polyamic acid R-2]
A polyamic acid R-2 solution was prepared in the same manner as in Comparative Synthesis Example 1 except that 6FDA was changed to PMDA shown in the following table as the acid anhydride.

[Comparative Synthesis Example 3]
According to the synthetic procedure described in Comparative Example 2 of JP-A-2003-084435, 3,3′,4,4′-diphenyl ether tetracarboxylic acid dianhydride (ODPA) and 4,4′-diaminodiphenyl ether (DDE, ODA). ) And ethanol (EtOH) were used to synthesize a 100% esterified polyamic acid ester to prepare a polyamic acid ester R-3 solution.

(Examples 1 , 2, 4 , 7, 8, 10 , 11, 13 , 15, 16, 18, 21, 22, 24, 25, 27, Reference Examples 3, 5, 6 , 9, 12 , 14, 17) , 19, 20, 23, 26 , 28, Comparative Examples 1 to 3).
In the mixing ratios (mass ratios) shown in Tables 23 and 24 below, a photobase generator was added to and dissolved in the polyamic acid ester and the solution of the polyamic acid obtained above, and the Examples and Reference Examples are shown. And the photosensitive resin composition of the comparative example was obtained. The photobase generator was added so as to be 10% by mass based on the total amount of the photosensitive resin composition. In addition, the compounding amount of the polyamic acid ester and the polyamic acid in the table shows the solid content.

＊１：イオン型１：和光純薬工業社製ＷＰＢＧ−１６７
＊２：イオン型２：和光純薬工業社製ＷＰＢＧ−１６８

＊３：非イオン型：桂皮酸アミド

*1: Ion type 1: WPBG-167 manufactured by Wako Pure Chemical Industries, Ltd.
*2: Ion type 2: WPBG-168 manufactured by Wako Pure Chemical Industries, Ltd.

*3: Nonionic type: cinnamic acid amide

[Pattern film formation method]
Each of the photosensitive resin compositions of Examples , Reference Examples and Comparative Examples was spin-coated on a wafer so that the film thickness after drying was 5 μm, and dried on a hot plate at 80° C. for 20 minutes.
A pattern mask was placed on the obtained dried film, and broad exposure was performed with a tabletop exposure apparatus (manufactured by Sanei Denki Co., Ltd.) at the exposure amounts shown in Tables 23 and 24.
After heating the wafer on a hot plate at 150° C. for 6 minutes, an organic solvent developer (DMAc (dimethylacetamide)) or an alkali developer (2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution and 2 It was developed by immersing it in a 1:1 weight ratio mixed solution of propanol).

[Resolution evaluation]
As the evaluation of resolution, the pattern after the development was observed with an electron microscope, and the size of the smallest shape that was well resolved in the pattern formation was evaluated.
Number: Minimum pattern size (μm)
×: Pattern cannot be formed

From the results shown in Tables 23 and 24, it is understood that the photosensitive resin composition of the present invention can provide a patterned film. Further, the composition containing the ionic photobase generator had higher sensitivity and better resolution than the nonionic photobase generator. Furthermore, by using a polyamic acid Tert-butyl ester and performing alkali development, there was an effect of promoting dissolution of the unexposed area, and better pattern formation was possible.
On the other hand, in the photosensitive resin composition of Comparative Example in which another polyamic acid or polyamic acid ester was blended in place of the specific polyamic acid ester in the present invention, it was difficult to form a pattern film.

Claims (5)

(A) polyamic acid ester,
A photosensitive resin composition containing (B) a photobase generator, comprising:
(A) the polyamic acid ester, have a structure represented by the following general formula (1),
(B) the photobase generating agent, a photosensitive resin composition characterized der Rukoto ionic photobase generator.

(In formula (1),
R ₁ is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, a tetravalent organic group containing an aromatic group and an alicyclic hydrocarbon group, or 4 containing a fluorine atom. Is a valent organic group,
R ₂ is any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group,
X is a divalent organic group,
R ₃ and R ₄ , which may be the same or different from each other, are a monovalent organic group or a functional group having silicon,
m is an integer of 1 or more,
n is 0 or an integer of 1 or more. ) The photosensitive resin composition according to claim 1, wherein the (A) polyamic acid ester has a structure represented by at least one of the following general formulas (1-1) and (1-2). ..

(In formula (1-1),
R ₂ is any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group,
X is a divalent organic group,
R ₃ and R ₄ , which may be the same or different from each other, are a monovalent organic group or a functional group having silicon,
m is an integer of 1 or more,
n is 0 or an integer of 1 or more. )

(In formula (1-2),
R ₂ is any of a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, and an alkylene group,
X is a divalent organic group,
R ₃ and R ₄ , which may be the same or different from each other, are a monovalent organic group or a functional group having silicon,
m is an integer of 1 or more,
n is 0 or an integer of 1 or more. ) A dry film having a resin layer obtained by applying the photosensitive resin composition according to claim 1 or 2 to a film and drying the film. A cured product obtained by curing the photosensitive resin composition according to claim 1 or 2 or the resin layer of the dry film according to claim 3 . A printed wiring board comprising the cured product according to claim 4 .