CN108475023B

CN108475023B - Photosensitive resin composition, dry film, cured product and printed wiring board

Info

Publication number: CN108475023B
Application number: CN201780005966.6A
Authority: CN
Inventors: 郭扬眉; 三轮崇夫; 冈安克起
Original assignee: Taiyo Holdings Co Ltd
Current assignee: Taiyo Holdings Co Ltd
Priority date: 2016-01-13
Filing date: 2017-01-12
Publication date: 2022-02-25
Anticipated expiration: 2037-01-12
Also published as: KR20180102622A; WO2017122744A1; CN108475023A; TWI735508B; JP6738353B2; JPWO2017122744A1; TW201738654A

Abstract

Providing: 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 the resin layer of the dry film, and a printed wiring board having the cured product. A photosensitive resin composition, and the like, the photosensitive resin composition being characterized by containing: (A) a polyamic acid ester and (B) a photobase generator, wherein the polyamic acid ester (A) has a structure represented by the following general formula (1). (in the formula (1), R₁Is a 4-valent organic radical, R₂Is any of a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton bonded with an alkylene group, and an alkylene group, X is a 2-valent organic group, R is₃And R₄Optionally identical to or different from each other, is a 1-valent organic group or a 1-valent functional group having silicon, m is an integer of 1 or more, and n is 0 or an integer of 1 or more. )

Description

Photosensitive resin composition, dry film, cured product and printed wiring board

Technical Field

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

Background

Polyimide is widely used in various fields because of its excellent properties such as high insulation, heat resistance, and high mechanical strength. For example, not only in the aerospace field of the first application, but also in the application to a coating film for a semiconductor device, a flexible printed circuit board, and a heat-resistant insulating interlayer material.

The polyimide has the following aspects: lack of thermoplasticity and solubility in organic solvents, processing difficulties. Therefore, polyimide is widely used by the following method: a photosensitive resin composition obtained by mixing a polyimide precursor such as polyamic acid or polyamic acid ester and a photoreactive compound is irradiated with active light and developed to form a desired pattern film, and then subjected to ring closure at high temperature to perform imidization (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 alkali-generating agent. 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 by irradiation with radiation.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 5-197148

Patent document 2: japanese patent laid-open publication No. 2003-084435

Disclosure of Invention

Problems to be solved by the invention

In recent years, with the advancement and densification of semiconductor mounting technologies, further miniaturization of polyimide pattern films has been demanded.

Accordingly, 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 the resin layer of the dry film, and a printed wiring board having the cured product.

Means for solving the problems

The present inventors have conducted extensive studies in view of the above, and as a result, have found that: the above problems can be solved by using a polyamic acid ester having a specific structure, and the present invention has been completed.

That is, the photosensitive resin composition of the present invention is characterized by containing (a) a polyamic acid ester having a structure represented by the following general formula (1) and (B) a photobase generator.

(in the formula (1), R₁Is a 4-valent organic radical, R₂Is any of a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton bonded with an alkylene group, and an alkylene group, X is a 2-valent organic group, R is₃And R₄Optionally identical to or different from each other, is a 1-valent organic group or a 1-valent functional group having silicon, m is an integer of 1 or more, and n is 0 or an integer of 1 or more. )

The polyamic acid ester (a) in the photosensitive resin composition of the present invention contains substantially no amic acid moiety. That is, the polyamic acid ester (a) in the photosensitive resin composition of the present invention is different from the polyamic acid derivative containing both an amic acid moiety and an amic acid ester moiety described in japanese unexamined patent publication No. 2003-084435.

In the photosensitive resin composition of the present invention, R in the general formula (1) is preferably R₁Is a 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, a 4-valent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a 4-valent organic group containing a fluorine atom.

In the photosensitive resin composition of the present invention, the polyamic acid ester (A) preferably has a structure represented by at least one of the following general formulae (1-1) and (1-2).

(in the formula (1-1), R₂Is a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton bonded with an alkylene groupAny one of a group and an alkylene group, X is a 2-valent organic group, R₃And R₄Optionally identical to or different from each other, is a 1-valent organic group or a 1-valent functional group having silicon, m is an integer of 1 or more, and n is 0 or an integer of 1 or more. )

(in the formula (1-2),

R₂is any of a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton bonded with an alkylene group, and an alkylene group,

x is an organic group having a valence of 2,

R₃and R₄Optionally identical to or different from one another, are 1-valent organic radicals or 1-valent functional groups with 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 photobase generator (B) is preferably an ionic photobase generator.

The dry film of the present invention is characterized by comprising 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 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.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, there can be provided: 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 the resin layer of the dry film, and a printed wiring board having the cured product.

Detailed Description

The components contained in the photosensitive resin composition of the present invention will be described in detail below.

[ (A) Polyamide acid ester ]

The polyamic acid ester (a) used in the present invention has a structure represented by the following general formula (1).

(A) The polyamic acid ester preferably has a number average molecular weight of 1000 to 100 ten thousand, more preferably 5000 to 50 ten thousand, and further preferably 1 to 20 ten thousand.

In the formula (1), R₁The organic group having a valence of 4 is not particularly limited and may be selected according to the use. 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. R₁The substituent R contained in the acid dianhydride described later used for producing the polyamic acid ester (A) is preferably₁。

In addition, when a patterned film is formed using a photosensitive resin composition with short-wavelength light, R is the number R from the viewpoint of absorption characteristics of the polymer₁Preferably, aliphatic groups are used.

In the present invention, R is R from the viewpoint of resolution₁Particularly preferred is a 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring, a 4-valent organic group containing an aromatic group and an alicyclic hydrocarbon group, or a 4-valent organic group containing a fluorine atom.

As R₁The 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring in (1) is preferably represented by any one of the following groups:

formula (1-1):

Z₁is a heel and Z₂The common ethylene groups together form an unsaturated hydrocarbon group having 4 to 12 carbon atoms of an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring), and the aromatic ring may have at least 1 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 hydroxyl group, or a halogen atom as a substituent.

Z₂Is a heel and Z₁The common ethylene groups together form an aliphatic hydrocarbon group having 3 to 10 (preferably 4 to 6, particularly 4) carbon atoms of an aliphatic hydrocarbon ring (alicyclic hydrocarbon), and the aliphatic hydrocarbon ring may have at least 1 alkyl group (having 1 to 4 carbon atoms), alkoxy group (having 1 to 4 carbon atoms), aryl group (having 6 to 10 carbon atoms), hydroxyl group, or halogen atom as a substituent. 2-1 valent atomic bonds (i.e., a set of atomic bonds, Z)₂The right-hand atom bond) are preferably bonded to adjacent carbons, "═ CR₆The 2-valent atomic bond represented by the- "is preferably bonded to the adjacent carbon atom of the adjacent carbon atom to which the 2" - "atomic bonds are bonded or the adjacent carbon atom thereof. The latter is particularly preferred. For example, when the aliphatic hydrocarbon ring is a cyclohexane ring, it is preferable that 2 "-" atoms are bonded to the 3, 4-positions, "-" (CR)₆- "is bonded in the 2 or 1 position (preferably the 1 position). R₆Generally, the hydrogen atom, alkyl group (having 1 to 4 carbon atoms), alkoxy group (having 1 to 4 carbon atoms), hydroxyl group, and halogen atom are preferable.

Formula (1-2):

Z₃is a heel and Z₄The common ethylene groups together form an unsaturated hydrocarbon group having 4 to 12 carbon atoms of an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring), and the aromatic ring may have at least 1 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 hydroxyl group, or a halogen atom as a substituent.

Z₄Is a heel and Z₃The common ethylene groups together form an aliphatic hydrocarbon group having 3 to 10 (preferably 4 to 6, particularly 4) carbon atoms of an aliphatic hydrocarbon ring (alicyclic hydrocarbon), and the aliphatic hydrocarbon ring may have at least 1 alkyl group (having 1 to 4 carbon atoms), alkoxy group (having 1 to 4 carbon atoms), aryl group (having 6 to 10 carbon atoms), hydroxyl group, or halogen atom as a substituent. 2-1 valent atomic bonds (a group of atomic bonds, Z)₄The right-hand group of atomic bonds or the left-hand group of atomic bonds) to adjacent carbons, the groups of atomic bonds may be arranged adjacent to each other, and if the ring is large, the groups may be arranged with at least 1 carbon atom interposed therebetween.

Formula (1-3):

Z₅is a heel and Z₆The common ethylene groups together form an unsaturated hydrocarbon group having 4 to 12 carbon atoms of an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring), and the aromatic ring may have at least 1 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 hydroxyl group, or a halogen atom as a substituent. The 1-valent atomic bonds shown by 2 "-" are bonded to adjacent carbons, and combinations of adjacent 1-valent atomic bonds shown by 2 "-" may be arranged adjacent to each other, and if the ring is large, they may be arranged with at least 1 carbon atom interposed therebetween. 2 of the atoms having a valence of 1 as represented by "-" are bonded to adjacent carbons, "- (CR)₇The 2-valent atomic bond represented by the- "is preferably bonded to an adjacent carbon atom through at least 1 carbon atom of the carbon to which the atomic bond of the" - "is bonded. R₇Generally, the hydrogen atom, alkyl group (having 1 to 4 carbon atoms), alkoxy group (having 1 to 4 carbon atoms), hydroxyl group, and halogen atom are preferable.

Z₆Is a heel and Z₅The common ethylene groups together form an aliphatic hydrocarbon group having 3 to 10 (preferably 4 to 6, particularly 4) carbon atoms of an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring), and the saturated hydrocarbon ring may have at least 1 alkyl group (having 1 to 4 carbon atoms), alkoxy group (having 1 to 4 carbon atoms), aryl group (having 6 to 10 carbon atoms), hydroxyl group, or halogen atom as a substituent.

Formula (1-4):

Z₇is a heel and Z₈The common ethylene groups together form an unsaturated hydrocarbon group having 4 to 12 carbon atoms of an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring), and the aromatic ring may have at least 1 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 hydroxyl group, or a halogen atom as a substituent. 2-1 valent atomic bonds (Z)₇The right-hand atomic bond of (A), or Z₇The left-hand atomic bonds of (b) are bonded to adjacent carbons, the atomic bonds of a group may be arranged adjacent to each other, and if the ring is large, the rings may be arranged with at least 1 carbon atom interposed therebetween.

Z₈Is a heel and Z₇The common ethylene groups together form a saturated hydrocarbon group having 3 to 10 (preferably 4 to 6, particularly 4) carbon atoms of an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring), and the saturated hydrocarbon ring may have at least 1 alkyl group (having 1 to 4 carbon atoms), alkoxy group (having 1 to 4 carbon atoms), aryl group (having 6 to 10 carbon atoms), hydroxyl group, or halogen atom as a substituent.

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

The aforementioned organic group having a valence of 4 and containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthyl group, and particularly a phenyl group), preferably has a trifluoromethyl group and an aromatic group.

The polyamic acid ester (A) preferably has a structure represented by at least one of the following general formulae (1-1) and (1-2).

(in the formula (1-1), R₂～R₄X, m and n are the same as those in formula (1). )

(in the formula (1-2), R₂～R₄X, m andn is the same as in formula (1). )

In the present invention, R in the formula (1)₂Is any of a group having an alicyclic skeleton, a phenylene group, a group having a biphenylene skeleton bonded with an alkylene group, and an alkylene group. The aforementioned phenylene group and alkylene group are each represented by the formula (1) with R₂The 2 nitrogen atoms bonded are directly bonded. On the other hand, the alicyclic skeleton and the biphenylene skeleton bonded with an alkylene group may be bonded to R in the formula (1)₂The 2 nitrogen atoms bonded are directly bonded or not directly bonded. R₂Preferably (A) the substituent R contained in the diamine or diisocyanate described later used for producing the polyamic acid ester₂。

R₂The group having an alicyclic skeleton in (1) may have a substituent or 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, R₁₀Is an aliphatic group, preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group, R₁₁Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group. )

R₂The phenylene group in (1) may have a substituent or may form a fused 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, R₁₂Each independently represents an aliphatic group or an aromatic group, and preferably represents an aliphatic group such as a methyl group or an ethyl group. )

R₂The aforementioned group having a biphenylene skeleton bonded with an alkylene group may have a substituent or may form a condensed ring. The aforementioned group having a biphenylene skeleton bonded with an alkylene group is preferably represented by the following general formula (2-3).

(in the formula (2-3), n3 and n4 each independently represents an integer of 0 to 4, R₁₃And R₁₄Each independently is an aliphatic group or an aromatic group, preferably an aliphatic group such as methyl or ethyl, R₁₅Represents an alkylene group having 1 to 5 carbon atoms. )

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

R₂The alkylene group in (1) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. In addition, R is₂The alkylene group in (2) may have a substituent such as an aliphatic group or an aromatic group.

For excellent resolution, R₂The group having an alicyclic skeleton is preferable, and the group having an alicyclic skeleton and no aromatic skeleton is more preferable.

In the present invention, R in the formula (1)₃And R₄Each independently is a 1-valent organic group or a 1-valent functional group having silicon. As R₃And R₄Examples of the organic group having a valence of 1 in (1) include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. As R₃And R₄Examples of the 1-valent silicon-containing functional group in (2) include a siloxane group, a silane group, and a silanol group.

R in the formula (1) is from the viewpoint of solubility at the time of synthesis of polyamic acid ester₃And R₄Alkyl groups are preferred. 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. Alkyl is here preferably butyl, pentyl or hexyl.

In the present invention, X in formula (1) is a 2-valent organic group, and examples thereof include: and a group containing an aromatic or aliphatic ester group, an amide imide group, a siloxane group, an epoxy group, an oxetanyl group, or the like as at least a part of the constituent.

(A) The polyamic acid ester may be used alone in 1 kind, or may be used in combination in 2 or more kinds. In addition, may be R₁And R₂At least any one of which comprises a copolymer of multiple structures.

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

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

The half ester obtained by reacting the acid anhydride with an alcohol is reacted with a diisocyanate such as isophorone diisocyanate to obtain (a) a polyamic acid ester. The synthesis method using diisocyanate allows the polyamic acid ester (a) to be synthesized more easily than the synthesis method using diamine.

(A) The acid anhydride used for synthesizing the polyamic acid ester is preferably a carboxylic acid dianhydride, and more preferably a tetracarboxylic acid dianhydride. Examples thereof include those represented by the following general formula (3).

(R in the formula₁As described in formula (1). )

By using the acid anhydride of the general formula (3) as a raw material for the synthesis of the polyamic acid ester (A), R in the repeating unit in the polyamic acid ester of the general formula (1) can be easily introduced₁And (4) a base.

Specific examples of the acid dianhydride that can be used for the synthesis of the polyamic acid ester (a) include aliphatic tetracarboxylic dianhydrides such as ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, methylcyclobutane tetracarboxylic dianhydride, and cyclopentane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3', 4, 4' -benzophenonetetracarboxylic dianhydride, 2 ', 3,3' -benzophenonetetracarboxylic dianhydride, 2, 3', 3, 4' -benzophenonetetracarboxylic dianhydride, 3,3', 4, 4' -biphenyltetracarboxylic dianhydride, 2 ', 3,3' -biphenyltetracarboxylic dianhydride, 2, 3', 3, 4' -biphenyltetracarboxylic dianhydride, 2 ', 6, 6' -biphenyltetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, bis (3, 4-dicarboxyphenyl) sulfone dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, Bis (2, 3-dicarboxyphenyl) methane dianhydride, bis (3, 4-dicarboxyphenyl) methane dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane dianhydride, 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-bis {4- [4- (1, 2-dicarboxy) phenoxy ] phenyl } propane dianhydride, 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 '-bis [4- (1, 2-dicarboxy) phenoxy ] biphenyl dianhydride, 4' -bis [3- (1, 2-dicarboxy) phenoxy ] biphenyl dianhydride, bis {4- [4- (1, 2-dicarboxy) phenoxy ] 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-bis {4- [4- (1, 2-dicarboxy) phenoxy ] phenyl } -1,1,1,3,3, 3-hexafluoropropane dianhydride, 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, aromatic tetracarboxylic acid dianhydrides such as 5, 8-naphthalenetetracarboxylic acid dianhydride, 1,2,5, 6-naphthalenetetracarboxylic acid dianhydride, 1,2,3, 4-benzenetetracarboxylic acid dianhydride, 1,2,4, 5-benzenetetracarboxylic acid dianhydride, 3,4,9, 10-perylenetetracarboxylic acid dianhydride, 2,3,6, 7-anthracenetetracarboxylic acid dianhydride, 1,2,7, 8-phenanthrenetetracarboxylic acid dianhydride, pyridinetetracarboxylic acid dianhydride, sulfonyldiphthalic anhydride, m-terphenyl-3, 3', 4, 4' -tetracarboxylic acid dianhydride, p-terphenyl-3, 3', 4, 4' -tetracarboxylic acid dianhydride, 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] furan-1, 3-diketones, and the like.

Among the above acid dianhydrides, tetracarboxylic acid dianhydride is preferably pyromellitic acid dianhydride, 3,3', 4, 4' -benzophenonetetracarboxylic acid dianhydride, 3,3', 4, 4' -biphenyltetracarboxylic acid dianhydride, 2 ', 6, 6' -biphenyltetracarboxylic acid dianhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 2-bis (3, 4-dicarboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane dianhydride, 1,2,4, 5-benzenetetracarboxylic acid dianhydride, 1,3,3a,4,5,9 b-hexahydro-5 (tetrahydro-2, 5-dioxo-3-furanyl) naphtho [1,2-c ] furan-1, 3-dione.

In addition, R in the formula (3)₁In the acid dianhydride which is a 4-valent organic group containing a fused ring of an aromatic ring and an aliphatic hydrocarbon ring or a 4-valent organic group containing an aromatic group and an alicyclic hydrocarbon group, the cyclic aliphatic skeleton is preferably a cyclohexane skeleton. The acid anhydride preferably has no alkyl group (e.g., 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 preferred.

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

(A) In the synthesis of polyamic acid ester, acid anhydride may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When acid dianhydride in which fluorine is introduced and acid dianhydride having an alicyclic skeleton are used in combination, physical properties such as solubility and thermal expansion coefficient can be adjusted without significantly impairing transparency. Further, if a rigid acid dianhydride such as pyromellitic dianhydride, 3', 4, 4' -biphenyltetracarboxylic dianhydride, or 1,4,5, 8-naphthalenetetracarboxylic dianhydride is used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but the improvement of transparency tends to be inhibited, and therefore, the polyimide can be used in combination while paying attention to the copolymerization ratio.

The diamine that can be used for obtaining the polyamic acid ester (a) includes a diamine represented by the following general formula (4). However, the following diamines are examples, and known diamines may be used without departing from the spirit of the present invention.

H₂N-R₂-NH₂ (4)

(in the formula, R₂As described in formula (1). )

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

Examples of the diisocyanate that can be used to obtain the polyamic acid ester (a) include diisocyanates represented by the following general formula (5). However, the following diisocyanates are examples, and known diisocyanates can be used without departing from the spirit of the present invention.

OCN-R₂-NCO (5)

(in the formula, R₂Is described in formula (1). )

Examples of the diisocyanate include isophorone diisocyanate (ITI), Toluene Diisocyanate (TDI), methylene diphenyl 4, 4' -diisocyanate (MDI), 2-bis (4-isocyanatophenyl) hexafluoropropane, and hexamethylene diisocyanate (HMDI).

[ (B) photobase generators ]

(B) The photobase generator is a compound as follows: a compound which changes its molecular structure by irradiation with light such as ultraviolet light or visible light, or which generates 1 or more basic substances acting as a catalyst for the ring-closure reaction of polyamic acid ester by molecular cleavage. (B) The photobase generator may be an ionic photobase generator or a nonionic photobase generator, and a composition of the ionic photobase generator is preferable because it has high sensitivity and excellent resolution and is advantageous for forming a pattern film. Examples of the basic substance include secondary amines and tertiary amines.

(nonionic photobase generators)

Examples of the nonionic photobase generator (B) include α -aminoacetophenone compounds, oxime ester compounds, and compounds having a substituent such as an N-formylated aromatic amino group, an N-acylated aromatic amino group, a nitrobenzylcarbamate group, or an alkoxybenzylcarbamate group.

As other photobase generators, WPBG-018 (trade name: 9-alkylmethyl N, N' -dimethyllcarbamate), WPBG-027 (trade name: (E) -1- [3- (2-hydroxyphenoyl) -2-propenoyl ] piperidine), WPBG-140 (trade name: 1- (alkylquinon-2-yl) ethyl imidocarboxylato), WPBG-165, and the like can be used.

The α -aminoacetophenone compound has a benzoin ether bond in the molecule, and when irradiated with light, causes intramolecular cleavage to generate a basic substance (amine) that exerts a curing catalytic action. Specific examples of the α -aminoacetophenone compound include commercially available compounds such as (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, manufactured by BASF Japan ltd.), 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan ltd.), 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone (Irgacure 379, trade name, manufactured by BASF Japan ltd.), and solutions thereof.

Any oxime ester compound can be used as long as it generates a basic substance by light irradiation. The oxime ester compound preferably has a group represented by the following general formula (6).

(in the formula, R¹⁶Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which is unsubstituted or substituted with a phenyl group or a halogen atom, an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with 1 or more hydroxyl groups, the alkyl group interrupted with 1 or more oxygen atoms, a cycloalkyl group having 5 to 8 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group, an alkanoyl group having 2 to 20 carbon atoms or a benzoyl group which is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group,

R¹⁷represents an unsubstituted or C1-6 alkyl group, a phenyl group or a phenyl group substituted with a halogen atom, an unsubstituted or C1-20 alkyl group substituted with 1 or more hydroxyl groups, the alkyl group interrupted with 1 or more oxygen atoms, a C5-8 cycloalkyl group unsubstituted or substituted with a C1-6 alkyl group or a phenyl group, or a C2-20 alkanoyl group or a benzoyl group unsubstituted or substituted with a C1-6 alkyl group or a phenyl group. )

The oxime ester compound may have a group represented by the following formula (7).

(in the formula, R¹⁸And R¹⁹Each independently hydrogen or a 1-valent organic group, which may be the same or different. In addition, 2 of them may be bonded to form a ring structure. )

Commercially available products of oxime ester photobase generators include CGI-325, Irgacure-OXE01, Irgacure-OXE02, N-1919, and NCI-831 manufactured by BASF Japan Ltd. Further, a compound having 2 oxime ester groups in the molecule as described in Japanese patent No. 4344400 can be suitably used.

Examples of the carbazole oxime ester compounds include those described in Japanese patent laid-open Nos. 2004-359639, 2005-097141, 2005-220097, 2006-160634, 2008-094770, 2008-509967, 2009-040762, and 2011-80036.

As the photobase generator (B), a photobase generator having a urethane structure represented by the following general formula (8) and photobase generators represented by the following general formulae (9) and (10) can be used.

(in the formula, R²⁰、R²¹、R²²And R²³Each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, an alkenyl group having 1 to 6 carbon atoms which may have a substituent, an alkynyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent (wherein R represents a group represented by the formula²⁰、R²¹、R²²And R²³At least one of which is not hydrogen), R²⁴And R²⁵Each independently represents hydrogen, an alkyl group having 1 to 6 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 8 carbon atoms which may have a substituent, an alkoxy group having 1 to 6 carbon atoms which may have a substituent, an alkenyl group having 1 to 6 carbon atoms which may have a substituent, an alkynyl group having 1 to 6 carbon atoms which may have a substituent, an aryl group which may have a substituent, a heterocyclic group which may have a substituent, a monocyclic ring which may have a substituent and is bonded to each other, or a polycyclic ring which may have a substituent and is bonded to each other, wherein R represents a group represented by formula (I), wherein R represents a group represented by formula (II)²⁶Represents a nitrophenyl group which may have a substituent, R²⁷And R²⁸Each independently represents hydrogen or an alkyl group having 1 to 6 carbon atoms which may have a substituent. )

(in the formula, R²⁹And R³⁰Each independently hydrogen or a 1-valent organic group, which may be the same or different. R²⁹And R³⁰They may be bonded to form a cyclic structure or may contain a bond of a hetero atom. Wherein R is²⁹And R³⁰At least 1 of which is a 1-valent organic group. R³¹、R³²、R³³And R³⁴Each independently hydrogen, halogen, hydroxy, nitro, nitroso, mercapto, silyl, silanol or 1-valent organic group, which may be the same or different. R³¹、R³²、R³³And R³⁴These 2 or more may be bonded to form a cyclic structure, and may contain a bond of a hetero atom. )

(in the formula (10), R³⁵Is unsubstituted or substituted by 1 or more alkyl, alkenyl, alkynyl, haloalkyl, NR⁴²R⁴³、CN、OR⁴⁴、SR⁴⁵、COR⁴⁶、COOR⁴⁷Halogen or a substituted aromatic or heteroaromatic group of formula (11);

alternatively, the first and second electrodes may be,

R³⁵is a group represented by the formula (12);

R³⁶and R³⁷Independently of each other, hydrogen, alkyl, alkenyl, alkynyl, OR unsubstituted OR substituted by 1 OR more alkyl, CN, OR⁴⁴、SR⁴⁵Halogen or haloalkyl substituted phenyl;

R³⁹is alkyl or NR^44AR^45A；R^44AAnd R^45AAre both unsubstituted or form an alkylene bridge substituted with 1 or more alkyl groups;

R³⁸、R⁴⁰、R⁴¹、R⁴²and R⁴³Independently of one another, hydrogen or alkyl; alternatively, the first and second electrodes may be,

R³⁸and R⁴⁰Are both unsubstituted or form an alkylene bridge substituted with 1 or more alkyl groups; or

R³⁹And R⁴¹From R³⁸And R⁴⁰Independently are both unsubstituted or form an alkylene bridge substituted with 1 or more alkyl groups;

R⁴⁴、R⁴⁵and R⁴⁷Independently of one another, hydrogen or alkyl;

R⁴⁶is hydrogen or alkyl; or unsubstituted or substituted by 1 or more alkyl, alkenyl, alkynyl, haloalkyl, NR⁴²R⁴³、CN、OR⁴⁴、SR⁴⁵、COR⁴⁴、COOR⁴⁷Or a halogen-substituted aromatic or heteroaromatic group;

R⁴⁸is unsubstituted or substituted by 1 or more alkyl, alkenyl, alkynyl, haloalkyl, NR⁴²R⁴³、CN、OR⁴⁴、SR⁴⁵、COR⁴⁶、COOR⁴⁷Or a halogen-substituted aromatic or heteroaromatic group;

R⁴⁹is hydrogen or alkyl;

R⁵⁰is hydrogen, alkyl, or unsubstituted or substituted by 1 or more alkyl, vinyl, alkenyl, alkynyl, haloalkyl, phenyl, NR⁴²R⁴³、CN、OR⁴⁴、SR⁴⁵、COR⁴⁶、COOR⁴⁷Or phenyl substituted with halogen. )

(Ionic photobase generator)

As the ionic photobase generator (B), for example, there can be used: a salt of an aromatic-component-containing carboxylic acid represented by the following general formula (13) with a tertiary amine, photobase generators represented by the following general formulae (14) to (18), (23) and (24), and ionic PBG produced by Wako pure chemical industries, Ltd, such as WPBG-082, WPBG-167, WPBG-168, WPBG-266 and WPBG-300.

(in the formula, R⁵¹～R⁶⁰Each independently hydrogen or a 1-valent organic group. )

(in the formula (14), Ar represents a group selected from the group consisting of the following general formula [ I ]]A coumarin group represented by the following general formula [ II ]]Any one group of the group consisting of acenaphthylene, Y⁺Represents a group selected from 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]A group represented by the following general formula [ VII]Z-represents a halogen anion, a borate anion, an N, N-dimethylcarbamate anion, an N, N-dimethyldithiocarbamate anion, a thiocyanate anion, a cyanate anion, a benzoate anion, or a benzoylformate anion, R⁶¹And R⁶²Each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a phenyl group which may have a substituent. )

(formula [ I ]]And formula [ II]In m, R⁶³And n R⁶⁴Each independently represents a halogen atom, a linear, branched or cyclic alkylcarbonyl group having 2 to 10 carbon atoms 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. )

(formula [ III ]]In, R⁶⁵～R⁶⁷Each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Formula [ IV]Wherein A represents a nitrogen atom or a methine group (CH group), R⁶⁸Represents a hydrogen atom or a hydroxyl group. General formula [ VII]In, R⁶⁹And R⁷⁰Each independently represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. )

(in the formulae (15) and (16), R⁷¹、R⁷²And R⁷³Each independently is a hydrogen atom or an organic group, and may be the same or different. R⁷¹、R⁷²And R⁷³They may be bonded to form a cyclic structure or may contain a bond of a hetero atom. Wherein R is⁷¹、R⁷²And R⁷³At least 1 of which is an organic group. R⁷⁴、R⁷⁶And R⁷⁷Each independently is a hydrogen atom or an organic group, and may be the same or different. R⁷⁵Is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a 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, a quaternary ammonium group or an organic group. R⁷⁴、R⁷⁵、R⁷⁶And R⁷⁷They may be bonded to form a cyclic structure or may contain a bond of a hetero atom. R⁷⁸And R⁷⁹Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, or an organic group, and may be the same or different. R⁸⁰、R⁸¹、R⁸²And R⁸³Each independently is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a thioether group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfinyl group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonate group, an amino group, a quaternary ammonium group or an organic group, and may be the same or different. R⁸⁰、R⁸¹、R⁸²And R⁸³These 2 or more may be bonded to form a cyclic structure, and may contain a bond of a hetero atom. R⁸⁴Protection of hydrogen atom or deprotection by at least either heating or irradiation of electromagnetic waveA group. )

(in the formulae (17) and (18), R⁸⁵And R⁸⁶Is alkyl group having 1 to 18 carbon atoms, alkenyl group having 2 to 18 carbon atoms, alkynyl group having 2 to 18 carbon atoms, aryl group having 6 to 14 carbon atoms, nitro group, hydroxyl group, cyano group, OR⁸⁷Alkoxy group shown, NR⁸⁸R⁸⁹Amino group shown as R⁹⁰Acyl group and R represented by CO⁹¹Acyloxy group or SR represented by COO⁹²Alkylthio or arylthio groups represented by the formula, or halogen atoms, R⁸⁷、R⁹⁰、R⁹¹And R⁹²Is C1-C8 alkyl or C6-C12 aryl, R⁸⁸And R⁸⁹Is 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⁺Is a quaternary ammonium group represented by any one of the following formulae (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, R is a tertiary amine group⁹³～R⁹⁵Is 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. R⁸⁵Or R⁸⁶And CH₂-Y⁺X^-The aromatic ring may be bonded to the same benzene ring or may be bonded to different benzene rings. X^-Is a counter anion selected from borate anions, phenolate anions and carboxylate anions. )

(in the formula (23), X¹、X²Independently represents an oxygen atom or a sulfur atom. R⁹⁶～R¹⁰⁴Independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or a 1-valent organic group. R¹⁰⁵、R¹⁰⁶、R¹⁰⁷Represents a hydrogen atom or a 1-valent organic group. Wherein R is¹⁰⁵、R¹⁰⁶、R¹⁰⁷In (1)At least 1 organic group having a valence of 1. )

(in the formula (24), R¹⁰⁸～R¹¹⁷Each independently is hydrogen or a 1-valent organic group, and 2 or more of them may be the same or completely different. In addition, 2 or more of them may be bonded to form a ring structure. R¹¹⁸～R¹²⁰Each independently represents hydrogen or a 1-valent organic group, and 2 or more of them may be the same or different. In addition, 2 or more of them may be bonded to form a ring structure. R¹²¹Hydrogen or a 1-valent organic radical. A is a compound or an element capable of forming an anion. )

The ionic PBG represented by the following structural formula, manufactured by Wako pure chemical industries, such as WPBG-082, WPBG-167, WPBG-168, WPBG-266, and WPBG-300, can be used.

WPBG-082

WPBG-167

WPBG-168

WPBG-266

WPBG-300

(B) The photobase generator can be used alone in 1 kind, and can also be used in combination in more than 2 kinds. (B) The amount of the photobase generator is preferably 5 to 50% by mass based on the total amount of the composition. When the content is 5 to 50% by mass, the resolution is more excellent.

When the coating film of the photosensitive resin composition is irradiated with active light, the combination and the amount of the (a) polyamic acid ester and the (B) photobase generator are appropriately selected depending on the thickness of the coating film so that the decomposition of the (B) photobase generator proceeds uniformly in the thickness direction. In order to achieve a low exposure and to cope with a thick film, it is preferable to use a polyamic acid ester (a) having a small absorption of the wavelength of the active light. The absorption characteristics can be appropriately changed by the molecular design of the polyamic acid ester (a). For example, in order to shift the absorption region to a short wavelength, (A) polyamic acid ester having an aromatic group is used to shorten the R₁And/or R₂And the like, or interfere with the formation of the charge-transporting complex.

Other components that can be blended in the photosensitive resin composition of the present invention will be 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) the polyamic acid ester, (B) the photobase generator, and other additives. Examples thereof include N, N '-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N' -dimethylacetamide, diethylene glycol dimethyl ether, cyclopentanone, γ -butyrolactone, α -acetyl- γ -butyrolactone, tetramethylurea, 1, 3-dimethyl-2-imidazoline, N-cyclohexyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, pyridine, γ -butyrolactone, and diethylene glycol monomethyl ether. These may be used alone, or 2 or more kinds may be mixed and used. The amount of the solvent to be used is not particularly limited, and may be used in the range of 50 to 9000 parts by mass per 100 parts by mass of the (a) polyamic acid ester, depending on the coating thickness and viscosity.

In order to further improve the photosensitivity, a sensitizer may be added to the photosensitive resin composition of the present invention. Examples of the sensitizer include Michler's ketone, 4 ' -bis (diethylamino) benzophenone, 2, 5-bis (4 ' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 ' -diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4 ' -dimethylaminobenzylidene) -4-methylcyclohexanone, 2, 6-bis (4 ' -diethylaminobenzylidene) -4-methylcyclohexanone, 4 ' -bis (dimethylamino) chalcone, 4 ' -bis (diethylamino) chalcone, p-dimethylaminocinnamoindanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminobhenylbiphenylene) -benzothiazole, 2- (p-dimethylaminobenylvinylene) benzothiazole, 2- (p-dimethylaminobenylidene) benzothiazole, 2-bis (4 ' -dimethylaminobenzylidene) -4-methylcyclohexanone, and p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1, 3-bis (4 '-dimethylaminobenzylidene) propanone, 1, 3-bis (4' -diethylaminobenzylidene) propanone, 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, N-p-tolyldiethanolamine, and mixtures thereof, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminostyryl) styrene and the like, and a thioxanthone such as 4- (1-methylethyl) -9H-thioxanthen-9-one is preferably used from the viewpoint of sensitivity. These may be used alone or in combination of 2 to 5 kinds. The sensitizer is preferably used in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the polyamic acid ester (A).

In addition, an adhesion promoter may be added to the photosensitive resin composition of the present invention in order to improve adhesion to a substrate. As the adhesion promoter, a known adhesion promoter may be used as long as it does not depart from the gist of the present invention. Examples thereof include γ -aminopropyldimethoxysilane, N- (. beta. -aminoethyl) - γ -aminopropylmethyldimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -mercaptopropylmethyldimethoxysilane, N- [3- (triethoxysilyl) propyl ] phthalimidic acid, and the reaction product of benzophenone tetracarboxylic dianhydride with (triethoxysilyl) propylamine. The amount of the adhesion promoter to be blended is preferably in the range of 0.5 to 10 parts by mass per 100 parts by mass of the polyamic acid ester (A).

In addition, an alkali proliferation agent may be added to the photosensitive resin composition of the present invention. In the case of forming a thick film pattern, the decomposition rate of the photobase generator (B) is required to be the same from the surface to the lower side. In this case, it is preferable to add an alkali growth promoter in order to improve the sensitivity. For example, the alkali proliferating agents disclosed in Japanese patent laid-open Nos. 2012 and 237776 and 2006 and 282657 can be used.

The photosensitive resin composition of the present invention may contain other photosensitive components that generate an acid by light, within a range that does not significantly impair the film characteristics after curing. When a compound having 1 or 2 or more ethylenically unsaturated bonds is added to the photosensitive resin composition of the present invention, a photoradical generator may be added.

In order to impart processing characteristics and various functionalities to the photosensitive resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. 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, and they may have a porous or hollow structure. Specific materials for obtaining porous shapes and hollow structures include various pigments, fillers, fibers, and the like.

The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention on a carrier film (support) and drying the same. The dry film was formed as follows: the photosensitive resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to an appropriate level, and then coated on a carrier film to a uniform thickness by a comma coater, a knife coater, a lip coater, a bar coater, a pressure coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, or the like. Then, the coated photosensitive resin composition is dried at a temperature of 50 to 130 ℃ for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, and is generally selected appropriately within a range of 10 to 150 μm, preferably 20 to 60 μm, in terms of the film thickness after drying.

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

After forming a resin layer containing the photosensitive resin composition of the present invention on a carrier film, a protective film that can be peeled off is preferably laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. Examples of the peelable protective film include a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and surface-treated paper. The protective film may be a film that is less than the adhesion between the resin layer and the carrier film when the protective film is peeled.

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

First, as step 1, a photosensitive resin composition is applied to a substrate and dried to obtain a coating film. As a method for applying the photosensitive resin composition to the substrate, a method used in the conventional application of the photosensitive resin composition, for example, a method of applying with a spin coater, a bar coater, a blade coater, a curtain coater, a screen printer, or the like, a method of spray-coating with a spray coater, an inkjet method, or the like can be used. As a method for drying the coating film, a method such as air drying, heat drying in an oven or a hot plate, or vacuum drying is used. Further, it is desirable that the coating film is dried under the condition that imidization of the polyamic acid ester (a) in the photosensitive resin composition does not occur. Specifically, the drying may be carried out by natural drying, forced air drying or heat drying at 20 to 140 ℃ for 1 minute to 1 hour. Preferably, drying is carried out on a hot plate for 1 to 20 minutes. Further, vacuum drying may be performed, and in this case, drying may be performed at room temperature for 1 minute to 1 hour.

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

Further, since imidization can be performed at a low temperature, the composition is characterized by being widely applicable to members and materials which are not suitable for high-temperature treatment, such as substrates of printed wiring boards.

Next, as step 2, the coating film is exposed through a photomask having a pattern or directly exposed. The exposure light is light having a wavelength which activates the photobase generator (B) to generate a base. When a sensitizer is used as appropriate as described above, the photosensitivity can be adjusted. As the exposure device, a contact aligner, a mirror projection, a step exposure device, a laser line exposure device, or the like can be used.

Next, as step 3, heating is performed so as to accelerate imidization of the coating film by the alkali generated in the coating film. Thus, the base generated in the exposed portion in the step 2 serves as a catalyst, and the polyamic acid ester (a) is partially imidized. The heating time and heating temperature are appropriately changed depending on the type of the polyamic acid ester (A), coating film thickness, and photobase generator (B) to be used. Typically, the coating thickness of about 10 μm is about 2 to 10 minutes at 110 to 200 ℃. When the heating temperature is too low, partial imidization cannot be effectively achieved. On the other hand, if the heating temperature is too high, imidization of the unexposed portions proceeds, and the difference in solubility between the exposed portions and the unexposed portions is reduced, which may hinder pattern formation.

Next, as step 4, the coating film is treated with a developer. Thus, a pattern film containing (a) a polyamic acid ester and a partially imidized polyimide can be formed on a substrate.

As a method used for the development, any method can be selected from conventionally known developing methods of photoresists, for example, spin coating, paddle method, dipping method with ultrasonic treatment, and the like. Examples of the developer include aqueous solutions of inorganic bases such as sodium hydroxide, sodium carbonate, sodium silicate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, and quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. If necessary, a suitable amount of a water-soluble organic solvent such as methanol, ethanol, or isopropyl alcohol, or a surfactant may be added to the mixture to form an aqueous solution. Thereafter, the coating film is washed with a washing liquid as necessary to obtain a patterned film. As the washing liquid, it can be used alone or in combination: distilled water, methanol, ethanol, isopropanol, and the like.

Further, as the developer, for example, organic solvents such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, γ -butyrolactone, hexamethylphosphoric triamide, methanol, ethanol, isopropanol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate, diacetone alcohol and the like can be used.

Thereafter, as step 5, the pattern film is heated. The heating temperature is set as appropriate so that the polyimide pattern film can be cured. For example, the heating is performed in an inert gas at 150 to 300 ℃ for about 5 to 120 minutes. The heating temperature is more preferably in the range of 150 to 250 ℃, and still more preferably in the range of 180 to 220 ℃. The heating is performed by using, for example, a hot plate, an oven, or an oven of an elevated temperature type capable of setting a temperature program. 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 various known fields and products using resin materials such as printing inks, adhesives, fillers, electronic materials, optical circuit components, molding materials, resist materials, building materials, three-dimensional shapes, optical members, and the like. In particular, the polyimide film is suitably used as a material for forming a wide range of fields and products in which the properties such as heat resistance, dimensional stability, and insulation property of the polyimide film are effective, for example, a paint or a printing ink, a wiring cover film such as a color filter, a film for a flexible display, a semiconductor device, an electronic component, an interlayer insulating film, and a solder resist, 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) a polyamic acid ester is mainly used as a pattern forming material (resist), and the pattern film formed therefrom functions as a component imparting heat resistance and insulation properties as a permanent film containing polyimide, and is suitable for forming, for example, a wiring cover film such as a color filter, a thin film for a flexible display, an electronic component, a semiconductor device, an interlayer insulating film, a solder resist, a cover film, a bank, an optical circuit component, an antireflection film, another optical component, or an electronic component.

Examples

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

Synthetic example 1: synthesis of Polyamic acid ester A-1

To 5g of 6FDA (4, 4' - (hexafluoroisopropylidene) diphthalic anhydride) as an acid dianhydride was added about 25g of dry MeOH and refluxed. Approximately 30 minutes after the start of reflux, a substantially clear liquid was obtained. Further, the mixture was refluxed for about 5 hours, cooled, and filtered through a filter having a pore diameter of 0.7 μm to remove impurities. Drying under reduced pressure, completely removing MeOH, and obtaining the half ester of the acid anhydride described in Table 1 as white crystals.

A three-necked flask having a capacity of 100ml was charged with 5mmol of the half ester of acid anhydride described in Table 1 and 0.0125mmol of 3-methyl-1-phenyl-2-phosphorus 1-oxide anhydride, and then dissolved in 10ml of dehydrated sulfolane while introducing nitrogen gas. 5mmol of anhydrous ITI (isophorone diisocyanate) as a diisocyanate was dissolved in 5ml of dehydrated sulfolane, and the solution was added dropwise to the flask over about 5 minutes. The mixed solution was reacted at 200 ℃ for 3 hours, and precipitated with MeOH (500 ml). The solution containing the precipitate was filtered and dried to obtain a high molecular precursor polymer. The resulting polymer was dissolved in DMAc (N, N-dimethylacetamide) and reprecipitated with MeOH. After filtration and drying, a 15 mass% polyamic acid ester A-1 solution was prepared using dehydrated DMAc as a solvent.

[ Table 1]

[ 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 6FDA was changed to PMDA (pyromellitic anhydride) as the acid dianhydride.

[ Table 2]

[ Synthesis example 3: synthesis of Polyamic acid ester A-3

A polyamic acid ester a-3 solution was prepared in the same manner as in synthesis example 1, except that the anhydrous ITI was changed to anhydrous MDI (4, 4' -methylenediphenyl diisocyanate) described in the following table.

[ Table 3]

[ 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 and anhydrous ITI was changed to anhydrous MDI shown in the following table as diisocyanate.

[ Table 4]

[ Synthesis example 5: synthesis of Polyamic acid ester A-5

A polyamic acid ester A-5 solution was prepared in the same manner as in Synthesis example 1, except that the diisocyanate ITI was changed to TDI-1(2, 4-tolylene diisocyanate) having a water content shown in the following Table.

[ Table 5]

[ 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 an acid dianhydride and anhydrous ITI was changed to anhydrous TDI-1 as a diisocyanate, which is shown in the following Table.

[ Table 6]

[ Synthesis example 7: synthesis of Polyamic acid ester A-7

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

[ Table 7]

[ 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 an acid dianhydride and anhydrous ITI was changed to anhydrous MDI as a diisocyanate as shown in the following Table.

[ Table 8]

[ 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 acid dianhydride.

[ Table 9]

[ Synthesis example 10: synthesis of Polyamic acid ester A-10

A polyamic acid ester a-10 solution was prepared in the same manner as in synthesis example 1, except that 6FDA was changed to PMDA and anhydrous ITI was changed to anhydrous HMDI (hexamethylene diisocyanate) described in the following table as diisocyanate.

[ Table 10]

[ 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 t-butanol in Synthesis example 1.

[ Table 11]

[ 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 t-butanol in Synthesis example 2.

[ Table 12]

[ 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 t-butanol in Synthesis example 3.

[ Table 13]

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 t-butanol in Synthesis example 4.

[ Table 14]

[ 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 t-butanol in Synthesis example 5.

[ Table 15]

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 t-butanol in Synthesis example 6.

[ Table 16]

[ 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 t-butanol in Synthesis example 7.

[ Table 17]

[ 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 t-butanol in Synthesis example 8.

[ Table 18]

[ 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 t-butanol in Synthesis example 9.

[ Table 19]

[ 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 t-butanol in Synthesis example 10.

[ Table 20]

Comparative synthesis example 1: synthesis of Polyamic acid R-1

In a separable flask having a capacity of 300ml, 30mmol of diamine described in the following table was charged, and the diamine was dissolved in dehydrated DMAc (N, N-dimethylacetamide) while flowing nitrogen gas. After the diamine was completely dissolved, 30mmol of 6FDA described in the following Table as an acid anhydride was slowly added. After 6FDA attached to the wall of the flask was poured into the reaction solution using a small amount of DMAc, the reaction solution was stirred at room temperature for 24 hours to obtain a 15 mass% polyamic acid solution. The amount of dehydrated DMAc charged was 75 mass% of the amount of the solution of polyamic acid.

[ Table 21]

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 described in the following table as an acid anhydride.

[ Table 22]

[ comparative Synthesis example 3]

A polyamic acid ester R-3 solution was prepared by synthesizing a 100% esterified polyamic acid ester using 3,3', 4,4 ' -diphenylethertetracarboxylic dianhydride (ODPA), 4,4 ' -diaminodiphenyl ether (DDE, ODA) and ethanol (EtOH) according to the synthesis procedure described in comparative example 2 of Japanese patent application laid-open No. 2003-084435.

Examples 1 to 28 and comparative examples 1 to 3

The solutions of the polyamic acid ester and the polyamic acid obtained above were mixed and dissolved with a photobase generator at the mixing ratios (mass ratios) described in tables 23 and 24 below to obtain photosensitive resin compositions of examples and comparative examples. The photobase generator is added so as to be 10 mass% based on the total amount of the photosensitive resin composition. In the table, the compounding amount of polyamic acid ester and polyamic acid indicates the solid content.

[ Table 23]

[ Table 24]

1, 1: ionic type 1: WPBG-167 manufactured by Wako pure chemical industries, Ltd

A, 2: ionic type 2: WPBG-168 manufactured by Wako pure chemical industries, Ltd

3, a: non-ionic: cinnamic acid amides

[ method for Forming Pattern film ]

The photosensitive resin compositions of examples and comparative examples were spin-coated on a wafer so that the film thickness after drying became 5 μm, and dried on a hot plate at 80 ℃ for 20 minutes.

A pattern mask was placed on the dried film, and a broad-band exposure was performed with exposure amounts shown in tables 23 and 24 using a bench exposure apparatus (manufactured by Sanyong Motor Co., Ltd.).

The wafer was heated on a hot plate at 150 ℃ for 6 minutes, and then immersed in an organic solvent developer (DMAc (dimethylacetamide)) or an alkali developer (a 1: 1 mixed solution of 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution and 2-propanol) for development.

[ evaluation of resolution ]

As an evaluation of the resolution, the pattern after the development was observed with an electron microscope, and the size of the minimum shape which was well resolved in the pattern formation was evaluated.

Numerical values: minimum pattern size (μm)

X: the patterning cannot be performed

From the results shown in tables 23 and 24, it was found that the photosensitive resin composition of the present invention can provide a patterned film. In addition, the composition containing the ionic photobase generator has higher sensitivity and better resolution than the nonionic photobase generator. Further, the alkali development using polyamide tert-butyl ester has an effect of promoting dissolution of unexposed portions, and thus enables more favorable pattern formation.

On the other hand, it is difficult to form a pattern film from the photosensitive resin composition of the comparative example containing the specific polyamic acid ester of the present invention and another polyamic acid or polyamic acid ester.

Claims

1. A photosensitive resin composition, comprising:

(A) polyamic acid ester, and

(B) a photobase-producing agent, which is a mixture of a photobase-producing agent,

the (A) polyamic acid ester has a structure represented by at least either of the following general formulae (1-1) and (1-2) and is free from an amic acid moiety,

in the formula (1-1),

x is an organic group having a valence of 2,

m is an integer of 1 or more,

n is an integer of 0 or 1 or more,

in the formula (1-2), the metal salt,

x is an organic group having a valence of 2,

m is an integer of 1 or more,

n is an integer of 0 or 1 or more;

the photobase generator (B) is an ionic photobase generator.

2. A dry film comprising a resin layer obtained by applying the photosensitive resin composition according to claim 1 to a film and drying the applied film.

3. A cured product obtained by curing the photosensitive resin composition according to claim 1 or the resin layer of the dry film according to claim 2.

4. A printed wiring board comprising the cured product according to claim 3.