TW201738654A - Photosensitive resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

Provided are 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. The photosensitive resin composition contains (A) a polyamic acid ester and (B) a photobase generator, the photosensitive resin composition, etc. being characterized in that the (A) a polyamic acid ester has a structure represented by general formula (1). (In formula (1), R1 is a tetravalent organic group; R2 is either a group having an alicyclic skeleton, a phenylene group, a group having a bisphenylene skeleton bonded with an alkylene group, or an alkylene group; X is a bivalent organic group; R3 and R4 may be the same or different from each other and are each either a monovalent organic group or a functional group having silicon; m is an integer of 1 or greater; and n is 0 or an integer of 1 or greater).

Description

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

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

Polyimine is widely used in various fields due to its excellent properties such as high insulation properties, heat resistance, and high mechanical strength. For example, it is not limited to the aerospace field originally applied, but is further applicable to a coating film of a semiconductor element or a flexible printed circuit board or a heat-resistant insulating interlayer.

Polyimine is one of the most difficult to process because of its thermoplasticity and lack of solubility in organic solvents. Therefore, the polyimide resin is prepared by irradiating active light rays with a photosensitive resin composition obtained by mixing a polyimide intermediate having a polyimide or a polyphthalamide precursor and a photoreactive compound. After the formation of a desired pattern film, a technique of applying a high temperature to form a ring closure to form a ruthenium is widely used (for example, Patent Documents 1 and 2).

For example, Patent Document 1 describes a photosensitive resin composition containing a polyphthalate and a photosensitive alkali generator. Further, Patent Document 2 describes a negative-type photosensitive resin containing a poly-proline derivative having both a proline moiety and a valinate moiety and a compound which generates a basic substance by irradiation with radiation. Composition.

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. Hei 5-119148

Patent Document 2: Japanese Laid-Open Patent Publication No. 2003-084435

Summary of invention

In recent years, with the increase in the size and density of semiconductor mounting technology, the pattern film of polyimine has been required to be finer.

Accordingly, an object of the present invention is to provide a photosensitive resin composition excellent in 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. Printed circuit board.

As a result of careful examination of the above, the present inventors have found that the above problems can be solved by using a polyamidoate having a specific structure, and the present invention has been completed.

That is, the photosensitive resin composition of the present invention contains a photosensitive resin composition of (A) polyphthalate and (B) a photobase generator, wherein the (A) polyphthalamide has The following general formula (1) The structure of the show.

(In the formula (1), R ₁ is a tetravalent organic group, and R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded by an alkyl group, and an alkyl group. Any one, X is a divalent organic group, and R ₃ and R ₄ are a monovalent organic group which may be the same or different from each other or a functional group having a fluorene, m is an integer of 1 or more, and n is an integer of 0 or more) .

Further, the (A) polyphthalate in the photosensitive resin composition of the present invention does not substantially contain a proline moiety. In other words, the (A) polyphthalate ester of the photosensitive resin composition of the present invention has both a proline moiety and a valinate moiety as described in JP-A-2003-084435. Poly-proline derivatives are different.

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

In the photosensitive resin composition of the present invention, the (A) polyphthalate is a structure having at least one of the following general formulae (1-1) and (1-2).

(In the formula (1-1), R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded to an alkyl group, and an alkyl group, and X is 2 a valence organic group, R ₃ and R ₄ are a monovalent organic group which may be the same or different from each other or a functional group having a fluorene, m is an integer of 1 or more, and n is an integer of 0 or more)

(In the formula (1-2), R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded to an alkyl group, and an alkyl group, and X is 2 The valence organic group, R ₃ and R ₄ are a monovalent organic group or a functional group having a fluorene which may be the same or different from each other, m is an integer of 1 or more, and n is an integer of 0 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 has a resin layer obtained by applying the photosensitive resin composition to a film and drying it.

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 circuit board of the present invention has the aforementioned hardened material.

According to the present invention, it is possible to provide a photosensitive resin composition excellent in 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 cured product having the cured product. A printed circuit board.

Form of implementing the invention

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

[(A) Polyurethane]

The (A) polyphthalate used in the present invention has a structure represented by the following formula (1).

(In the formula (1), R ₁ is a tetravalent organic group, and R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded by an alkyl group, and an alkyl group. Any one, X is a divalent organic group, and R ₃ and R ₄ are a monovalent organic group which may be the same or different from each other or a functional group having a fluorene, m is an integer of 1 or more, and n is an integer of 0 or more) .

(A) The preferred number average molecular weight of the polyglycolate is from 1,000 to 1,000,000, more preferably from 5,000 to 500,000, and even more preferably from 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 depending on the use. For example, an aromatic group is preferable, and an aromatic group having 6 to 32 carbon atoms or an aliphatic group is preferable, and an aliphatic group having 4 to 20 carbon atoms is preferable. R ₁ is preferably a substituent R ₁ contained in the acid dianhydride after the production of the (A) polyphthalate.

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

In the present invention, in particular, from the viewpoint of analytical properties, 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 The tetravalent organic group of the fluorine atom is preferred.

The tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring in R ₁ is preferably

Any one of the presenters.

Formula (1-1):

The Z _{1 group} and the Z ₂ coexisting ethyl group together form an aromatic hydrocarbon ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) having 4 to 12 carbon atoms, and the aromatic ring may have 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 hydroxyl group, and a halogen atom.

The Z ₂ system and the Z ₁ coexisting ethyl group together form an aliphatic hydrocarbon group having an aliphatic hydrocarbon ring (alicyclic hydrocarbon) having 3 to 10 carbon atoms (preferably 4 to 6, especially 4). The aliphatic hydrocarbon ring may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms) as a substituent. ), hydroxyl, halogen atom. Two "-" indicates that a bonding hand (that is, a set of bonding keys, a connecting key on the right side of Z ₂ ) is bonded to carbon adjacent to each other, but with "=CR ₆ - The two-valent linking bond is preferably bonded to an adjacent carbon atom adjacent to a carbon atom to which two "-" linkages are bonded, or an adjacent carbon atom. Especially the latter is better. For example, in the case where the aliphatic hydrocarbon ring is a cyclohexane ring, two "-" linkages are bonded to the 3, 4 positions, and "=CR ₆ -" is bonded at 2 or 1 position (preferably 1 position). good. R _{6 is} usually a hydrogen atom, an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxyl group or a halogen atom, and preferably a hydrogen atom.

Equation (1-2):

The Z _{3 group} and the Z ₄ coexisting ethyl group together form an aromatic hydrocarbon ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) having 4 to 12 carbon atoms, and the aromatic ring may have 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 hydroxyl group, and a halogen atom.

The Z _{4 group} and the Z ₃ coexisting ethyl group together form an aliphatic hydrocarbon group having an aliphatic hydrocarbon ring (alicyclic hydrocarbon) having 3 to 10 carbon atoms (preferably 4 to 6, especially 4). The aliphatic hydrocarbon ring may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms) as a substituent. ), hydroxyl, halogen atom. Two "-" indicates that the 1-valent link key (a set of link keys, a set of link keys on the right side of Z ₄ or a set of link keys on the left side) is bonded to each adjacent carbon, but a set of link keys can be When they are arranged adjacent to each other or the ring is large, at least one carbon atom may be placed in the mutual arrangement.

Formula (1-3):

The Z _{5 group} and the Z ₆ coexisting ethyl group together form an aromatic hydrocarbon ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) having 4 to 12 carbon atoms, and the aromatic ring may have 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 hydroxyl group, and a halogen atom. The one-valent link key represented by two "-"s is bonded to the adjacent carbon, but the combination of the one-valent bond keys represented by two "-"s may be adjacent to each other or the ring may be large. It can be placed by placing at least one carbon atom. The two "-"s indicate that the one-valent link key is bonded to the adjacent carbon, but the two-valent link key represented by "=CR _7- " is bonded to the "-" link key. At least one carbon atom is placed in the carbon, and adjacent carbon atoms are preferred. R _{7 is} usually a hydrogen atom, an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), a hydroxyl group or a halogen atom, and preferably a hydrogen atom.

An aliphatic hydrocarbon group having 3 to 10 (preferably 4 to 6, especially 4) carbon atoms of the aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) formed by the Z ₆ system and the Z ₅ coexisting ethyl group together The saturated hydrocarbon ring may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms) as a substituent. ), hydroxyl, halogen atom.

Formula (1-4):

The Z ₇ system and the Z ₈ coexisting ethyl group together form an aromatic ring (preferably a benzene ring, a naphthalene ring, particularly a benzene ring) having 4 to 12 carbon atoms in an unsaturated hydrocarbon group, and the aromatic ring may have 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 hydroxyl group, and a halogen atom as a substituent. 2 "-" represents the monovalent connecting bond (Z link key on the right of ₇ of, or Z linked keys to the left of of ₇₎ based bonded to the adjacent to the respective carbon, but the link key set it may be arranged adjacent to each other, When the ring is large, at least one carbon atom may be placed in the mutual arrangement.

The Z _{8 group} and the Z ₇ coexisting ethyl group together form an aliphatic hydrocarbon ring (alicyclic hydrocarbon ring) having 3 to 10 (preferably 4 to 6, especially 4) saturated hydrocarbon groups. The saturated hydrocarbon ring may have at least one alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), and an aryl group (having 6 to 10 carbon atoms) as a substituent. , hydroxyl, halogen atom.

Among the formulae (1-1) to (1-4), an organic group represented by the formulae (1-1) and (1-2) is preferred, and an organic group represented by the formula (1-1) is particularly preferred.

The tetravalent organic group containing a fluorine atom preferably has an aromatic group (preferably a phenyl group, a naphthyl group, particularly a phenyl group), and more preferably has a trifluoromethyl group and an aromatic group.

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

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

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

In the present invention, R ₂ in the formula (1) has an alicyclic skeleton group, a phenyl group, a group having a stretched diphenyl skeleton bonded to an alkyl group, and an alkyl group. Each of the above-mentioned phenylene and alkylene groups is directly bonded to the two nitrogen atoms bonded to R ₂ in the formula (1). Further, the alicyclic skeleton and the extended diphenyl skeleton bonded by the above alkyl group may be directly bonded to the two nitrogen atoms bonded to R ₂ in the formula (1), or may not be bonded. The substituent R ₂ contained in the diamine or diisocyanate described later for use in the production of the R ₂ -based (A) polyphthalate is preferred.

The group having the aforementioned alicyclic skeleton in R ₂ may have a substituent or may form a condensed ring. The group having the alicyclic skeleton is preferably represented by the following formula (2-1).

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

The aforementioned phenyl group in R ₂ may have a substituent or may form a condensed ring. The above-mentioned stretched phenyl group is preferably represented by the following formula (2-2).

(In the formula (2-2), n2 represents an integer of 0 to 4, and each of R _{12 is} independently an aliphatic group or an aromatic group, and preferably an aliphatic group such as a methyl group or an ethyl group.)

The group having a coextruded diphenyl skeleton bonded to the above alkyl group in R ₂ may have a substituent or may form a condensed ring. The group having a stretched diphenyl skeleton bonded to the above alkyl group is preferably represented by the following formula (2-3).

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

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

The alkylene group in R ₂ is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms. Further, the alkylene-based aliphatic group or the aromatic group in R ₂ may have a substituent.

R ₂ is excellent in analytic properties, preferably has an alicyclic skeleton, and has an alicyclic skeleton, and is more preferably a group having no aromatic skeleton.

In the present invention, R ₃ and R ₄ in the formula (1) are each independently a monovalent organic group or a functional group having a fluorene. Examples of the monovalent organic group in R ₃ and R ₄ include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. Examples of the monovalent functional group having a fluorene in R ₃ and R ₄ include a decyloxyalkyl group, a decylalkyl group, and a decyl alcohol group.

R ₃ and R ₄ in the formula (1) are preferably an alkyl group from the viewpoint of solubility in the synthesis of the polyphthalate. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or 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, and examples thereof include an aromatic or aliphatic ester group, a guanamine group, an amidoxime group, a decyloxy group, an epoxy group, An oxocyclobutyl group or the like is a constituent of at least a part.

(A) Polyacetamide may be used singly or in combination of two or more. Further, at least one of R ₁ and R ₂ may be a copolymer composed of a plurality of structures.

(A) The amount of the polyamidite to be used may be, for example, in the range of 5 to 30% by mass based on the total thickness of the coating film depending on the thickness or viscosity of the coating film.

(A) Polyphthalate can be synthesized by a conventional method. For example, an acid anhydride such as 3,3'-benzophenonetetracarboxylic dianhydride is reacted with an alcohol such as ethanol as a half ester. The half ester was ruthenium chloride as the diester diacid chloride. The (A) polyphthalate ester can be obtained by reacting the diester diacid chloride with a diamine such as 3,5-diaminobenzoic acid.

Further, (A) a polyphthalamide can also be obtained by reacting a half ester obtained by reacting the above acid anhydride with an alcohol with a diisocyanate such as isophorone diisocyanate. Further, compared with the synthesis method using the above diamine, the synthesis method of the diisocyanate can be used to synthesize (A) polyphthalate.

(A) The above-mentioned acid anhydride which can be used for the synthesis of polyphthalate is preferably a carboxylic acid dianhydride, more preferably a tetracarboxylic dianhydride. The following general formula (3) is shown.

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

By using the acid anhydride of the formula (3), as the synthetic raw material of the (A) polyphthalate, the R ₁ group in the repeating unit in the polyphthalate of the above formula (1) can be easily introduced.

Specific examples of the acid dianhydride which can be used for the synthesis of the above (A) polyphthalate include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methyl group. An aliphatic tetracarboxylic dianhydride such as cyclobutane tetracarboxylic dianhydride or cyclopentane tetracarboxylic dianhydride; pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-benzophenone tetracarboxylic dianhydride, 3,3',4 , 4'-biphenyltetracarboxylic 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 ( dianhydride ), 2,2-bis (2, 3-Dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 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)benzylidene]benzene , 1,4-bis[(3,4-dicarboxy)benzimidyl]phthalic anhydride, 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)benzene Oxy]phenyl}one dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}one dianhydride, 4,4'-bis[4-(1,2- Dicarboxy)phenoxy]biphenyl dianhydride, 4,4'-bis[3-(1,2-dicarboxy)phenoxy]biphenyl dianhydride, double {4-[4-(1, 2-Dicarboxy)phenoxy]phenyl}one dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}one dianhydride, double {4-[4-( 1,2-dicarboxy)phenoxy]phenyl}ruthenic anhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}phosphinic anhydride, double {4-[4 -(1,2-dicarboxy)phenoxy]phenyl}sulfide dianhydride, bis{4-[3-(1,2-dicarboxy)phenoxy]phenyl}thio dianhydride, 2 ,2-bis{4-[4-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-double { 4-[3-(1,2-dicarboxy)phenoxy]phenyl}-1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Acid 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 - perylene tetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonium sulfonate Diphthalic anhydride, m-terphenyl--3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride Aromatic tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene [1,2-c] Furan-1,3-dione and the like.

Among the above acid dianhydrides, tetracarboxylic dianhydride is preferably pyromellitic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3', 4 , 4'-biphenyltetracarboxylic dianhydride, 2,2',6,6'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2 - bis(3,4-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)naphthalene [1,2-c]furan-1,3-dione.

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

The above acid anhydride is preferably an acid anhydride group having a succinic anhydride structure. The acid anhydride group having a succinic anhydride structure may, for example, be an acid anhydride group as described below.

Among the above acid anhydrides, the following compounds are preferred.

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) polyglycolate, the acid anhydride may be used alone or in combination of two or more.

When the acid dianhydride used is an acid dianhydride introduced with fluorine or an acid dianhydride having an alicyclic skeleton, the transparency is less likely to be impaired, and the dissolution can be adjusted. Physical properties such as sex or thermal expansion rate. Further, when a straight acid dianhydride such as pyromellitic anhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride or 1,4,5,8-naphthalenetetracarboxylic dianhydride is used, The linear thermal expansion coefficient of the finally obtained polyimine is small, but there is a tendency to hinder the improvement of transparency, so that the copolymerization ratio can be used in combination.

In order to obtain the above-mentioned diamine which is useful for the (A) polyphthalate, a diamine represented by the following formula (4) can be mentioned. However, the following is an example, and a conventional person can be used without violating the object of the present invention.

H ₂ NR ₂ -NH ₂ (4)

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

The diamine may, for example, be diaminoisophorone (3-aminomethyl-3,5,5-trimethylcyclohexylamine), toluenediamine or 4,4'-methylenediphenyldiene. Amine, hexamethylene diamine, and the like.

The diisocyanate represented by the following general formula (5) is exemplified as the diisocyanate which can be used for the (A) polyphthalate. However, the following is an example, and a conventional person can be used without violating the object of the present invention.

OCN-R ₂ -NCO (5)

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

Examples of the aforementioned diisocyanate include isophorone diisocyanate (ITI), toluene diisocyanate (TDI), methylene diphenyl 4,4'-diisocyanate (MDI), and 2,2-bis (4). - Isocyanate phenyl) hexafluoropropane, hexamethylene diisocyanate (HMDI), and the like.

[(B) Photobase generator]

The photobase generator is formed by irradiating light such as ultraviolet light or visible light to change the molecular structure or by molecular cracking to form one or more bases capable of exhibiting a catalytic activity as a ring closure reaction of polyglycolate. a compound of a substance. (B) The photobase generator may be an ionic photobase generator or a nonionic photobase generator, but the ionic photobase generator has a high sensitivity to the composition, and is advantageous for forming an analytically excellent pattern film. Therefore, it is better. Examples of the basic substance include a secondary amine and a tertiary amine.

(non-ionic photobase generator)

The nonionic (B) photobase generator may, for example, be an α-aminoacetophenone compound, an oxime ester compound, or an N-methylated aromatic amine group, an N-deuterated aromatic amine group, or a nitrate. A compound such as a substituent such as a benzyl carbamic acid ester group or an alkoxybenzyl urethane group.

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

The α-aminoacetophenone compound has a benzoin ether bond in the molecule, and when exposed to light, cracks occur in the molecule to form a basic substance (amine) having a hardening catalyst action. As a specific example of the α-aminoacetophenone compound, (4-morpholinylbenzylidene)-1-benzyl-1-dimethylaminopropane can be used. (IRGACURE 369, trade name, manufactured by BASF JAPAN Co., Ltd.) or 4-(methylthiobenzimidyl)-1-methyl-1-morpholinylethane (IRGACURE 907, trade name, manufactured by BASF JAPAN Co., Ltd.), 2 -(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (IRGACURE 379, trade name, A commercially available compound such as BASF JAPAN Co., Ltd. or a solution thereof.

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

(wherein R ¹⁶ represents a hydrogen atom, a phenyl group which is unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, an unsubstituted or substituted carbon group having 1 or more hydroxyl groups of 1 to 20; An alkyl group, the alkyl group interrupted by one or more oxygen atoms, an unsubstituted or substituted alkyl group having a carbon number of 1 to 6 or a phenyl group, a cycloalkyl group having 5 to 8 carbon atoms, an unsubstituted or carbon number ～ alkyl or phenyl substituted with 2 to 20 carbon alkyl or benzhydryl groups, and R ₁₇ represents unsubstituted or substituted with a C 1 to 6 alkyl group, a phenyl group or a halogen atom. An alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with one or more hydroxyl groups, which is interrupted by one or more oxygen atoms, or is substituted or substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group. a cycloalkyl group having 5 to 8 carbon atoms, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms or a phenyl group, and a 2 to 20 carbon alkyl group or a benzamidine group.

Further, the oxime ester compound may be a group having the following formula (7).

(wherein 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 bonds may form a cyclic structure.)

Commercial products of the oxime ester-based photobase generator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF JAPAN Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., and NCI-831. Further, a compound having two oxime ester groups in the molecule described in Japanese Patent No. 4344400 can also be suitably used.

Others, Japanese Laid-Open Patent Publication No. 2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, and Japan The carbazole oxime ester compound described in JP-A-2008-80036, JP-A-2009-80036, and JP-A-2011-80036.

Further, (B) the photobase generator is a photobase generator having a urethane structure of the following formula (8), and photobase generation represented by the following formulas (9) and (10) may be used. Agent.

(wherein R ²⁰ , R ²¹ , R ²² and R ²³ each independently represent 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, Alkoxy group having 1 to 6 carbon atoms having 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 having a substituent, Or a heterocyclic group which may have a substituent (but at least one of R ²⁰ , R ²¹ , R ²² and R ²³ is not hydrogen), and R ²⁴ and R ²⁵ each independently represent a hydrogen, a carbon number which may have a substituent An alkyl group of 1 to 6, an alkyl 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 be bonded to each other and which may have a substituent, or which are bonded to each other a polycyclic ring which may have a substituent, wherein R ²⁶ represents a nitrophenyl group which may have a substituent, 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.

(wherein 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 may be bonded to form a cyclic structure or may contain a hetero atom bond. 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, hydroxy, nitro, nitroso, decyl, decyl, stanol The group or the monovalent organic group may be the same or different. Two or more of R ³¹ , R ³² , R ³³ and R ³⁴ may be bonded to form a cyclic structure or may contain a hetero atom bond.

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

Substituted aromatic or heteroaromatic group; or R ³⁵ system (12)

a group represented by R ³⁶ and R ³⁷ independently of hydrogen, alkyl, alkenyl, alkynyl or unsubstituted or substituted with one or more alkyl groups, CN, OR ⁴⁴ , SR ⁴⁵ , halogen or haloalkyl R ³⁹ is alkyl or NR ^44A R ^45A ; R ^44A and R ^45A are all unsubstituted or form an alkylene bridge substituted by one or more alkyl groups; R ³⁸ , R ⁴⁰ , R ⁴¹ , R ⁴² and R ^{43 are} each independently hydrogen or alkyl; or R ³⁸ and R ⁴⁰ are both unsubstituted or formed into an alkylene bridge substituted with one or more alkyl groups; or R ³⁹ and R ⁴¹ are from R ³⁸ And R ^{40 are} independently unsubstituted or form an alkylene bridge substituted by one or more alkyl groups; R ⁴⁴ , R ⁴⁵ and R ^{47 are} each independently hydrogen or alkyl; R ⁴⁶ is hydrogen or alkyl; An aromatic or heteroaromatic group substituted or substituted with one or more alkyl, alkenyl, alkynyl, haloalkyl, NR ⁴² R ⁴³ , CN, OR ⁴⁴ , SR ⁴⁵ , COR ⁴⁴ , COOR ⁴⁷ , or halogen R ⁴⁸ is an aromatic which is unsubstituted or substituted by more than one alkyl, alkenyl, alkynyl, haloalkyl, NR ⁴² R ⁴³ , CN, OR ⁴⁴ , SR ⁴⁵ , COR ⁴⁶ , COOR ⁴⁷ , or halogen an aromatic or heteroaromatic group; R ⁴⁹ is hydrogen or Group; R ⁵⁰ is hydrogen, alkyl, or unsubstituted or with one or more of alkyl, vinyl, alkenyl, alkynyl, haloalkyl, ^{phenyl, NR 42 R 43, CN,} OR 44, SR 45 , COR ⁴⁶ , COOR ⁴⁷ or halogen substituted phenyl. )

(ion type photobase generator)

For the ionic (B) photobase generator, for example, a salt of an aromatic component-containing carboxylic acid and a tertiary amine represented by the following formula (13), and the following formulas (14) to (18) and (23) can be used. And the photobase generator represented by (24), the WPBG-082, WPBG-167, WPBG-168, WPBG-266, WPBG-300, etc. of the ionic type PBG by the Wako Pure Chemical Company.

(wherein R ⁵¹ to R ⁶⁰ are each independently hydrogen or a monovalent organic group.)

(In the formula (14), Ar represents a group selected from the group consisting of a coumarinyl group represented by the following formula [I] and an acenaphthenyl group represented by the following formula [II]. Any one of Y ⁺ represents a group represented by the following formula [III], a group represented by the following formula [IV], a group represented by the following formula [V], and a formula represented by the following formula [VI]. And a group of any of the groups represented by the following formula [VII], Z ^- represents a halogen anion, a borate anion, an N,N-dimethylcarbamate anion, N,N- dimethyldithiocarbamate amino acid salts (dithiocarbamates) anion, thiocyanate anion, a cyanate anion, benzoic acid anion, carboxylate anion, or benzoyl group, R ⁶¹ and R ⁶² each independently represent 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.

(In the formula [I] and the formula [II], m R ⁶³ and n R ⁶⁴ each independently represent a halogen atom, a linear, branched or cyclic alkylcarbonyl group having 2 to 10 carbon atoms or a carbon number. a linear, branched or cyclic alkyl group of 1 to 10. m represents an integer from 0 to 5, and n represents an integer from 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 represents a nitrogen atom or a methine group ( CH group), R ⁶⁸ represents a hydrogen atom or a hydroxyl group of the general formula [VII] in, R ⁶⁹ and R ⁷⁰ each independently represent a hydrogen atom or 1 to 10 carbon atoms of straight-chain, branched, or cyclic alkyl group of. )

(In the formulae (15) and (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 form a ring. The structure may also contain a hetero atom bond. However, at least one of R ⁷¹ , R ⁷² and R ⁷³ is an organic group. R ⁷⁴ , R ⁷⁶ and R ⁷⁷ are each independently a hydrogen atom or an organic group, and may be the same or phase. R ⁷⁵ is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a sulfide ion group, a methyl group, a decyl group, a nitro group, a nitroso group, a phosphino group, a phosphinyl group, a phosphonium group, a phosphonium group, an amine. a group, an ammonium group or an organic group. R ⁷⁴ , R ⁷⁵ , R ⁷⁶ and R ⁷⁷ may be bonded to each other to form a cyclic structure or a bond of a hetero atom. R ⁷⁸ and R ⁷⁹ are each independently a hydrogen atom or a halogen. Atom, hydroxyl, sulfhydryl, thiol, methoxyalkyl, stanol, nitro, nitroso, sulfinyl, sulfo, sulfonate, phosphino, phosphinyl, phosphonium, phosphino , or an organic group, may be the same or different .R ^80, 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 methyl group silicon, silicon alkoxide group, a nitro , Nitroso, sulfinyl group, a sulfo group, a sulfonic acid group, a phosphino group, a phosphinyl group, a phosphorus acyl, acyl phosphine, an amine, an ammonium group or an organic group, may be the same or different .R ^80, R ⁸¹ , R ⁸² and R ⁸³ may form a cyclic structure or a hetero atom bond, and R ^{84 may} be a hydrogen atom or may be removed by heating or electromagnetic wave irradiation. Protected protection base.)

(In the formulae (17) and (18), R ⁸⁵ and R ⁸⁶ are 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 a carbon number of 6 to 14 An aryl group, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by OR ⁸⁷ , an amine group represented by NR ⁸⁸ R ⁸⁹ , a fluorenyl group represented by R ⁹⁰ CO, a decyl group represented by R ⁹¹ COO, and SR ⁹² An alkylthio or arylthio group or a halogen atom, 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, and 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 a formula (19) to (22) Any of the fourth-order ammonium groups represented by Q, 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, and A is a hydrogen atom, a hydroxyl group or a halogen atom, 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 may be bonded to the same as CH ₂ -Y ⁺ X ^- The benzene ring is bonded to a different benzene ring. X ^- is a counter anion selected from the group consisting of a borate anion, a Phenolate anion, and a carboxylate anion.

(In the formula (23), X ¹ and X ^{2 each} 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 thiol group, a nitro group, a decyl group, a decyl group, or 1 The valent organic group: R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ represent a hydrogen atom or a monovalent organic group, but at least one of R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ is a monovalent organic group.

(In the formula (24), R ¹⁰⁸ to R ¹¹⁷ are each independently hydrogen or a monovalent organic group, and two or more of them may be the same or all different. Further, two or more of them may be bonded to form a cyclic structure. 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. Further, two or more of them may be bonded to form a cyclic structure. R ¹²¹ is hydrogen or a monovalent organic group. A. A system can be an anionic compound or element.)

WPBG-082, WPBG-167, WPBG-168, WPBG-266, WPBG-300, etc. of the ionic PBG manufactured by Wako Pure Chemical Industries, Ltd. can be used.

(B) The photobase generator may be used alone or in combination of two or more. (B) The amount of the photobase generator is preferably from 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 combination of the (A) polyphthalate and the (B) photobase generator is added, the coating film thickness is appropriately selected, and the active light is applied to the coating film of the photosensitive resin composition in the thickness direction ( B) The photobase generator is uniformly decomposed. In order to achieve low exposure quantification, it is also possible to thicken the film. (A) Polyphthalate is preferably used for the wavelength of the active light, and the absorption is small. The absorption characteristics can be suitably changed by the molecular design of (A) polyphthalate. For example, in order to shift the absorption region to a short wavelength, the (A) polyphthalate having an aromatic group is used, which is advantageous for shortening the above-mentioned conjugated system of R ₁ and/or R ₂ or the like, or hinders the charge shifting complex. Formation.

The other components which can be blended in the photosensitive resin composition of the present invention will be described below.

The solvent which can be used in the photosensitive resin composition of the present invention is not particularly limited as long as it dissolves (A) polyphthalate, (B) photobase generator, and other additives. For example, N,N'-dimethylformamide, N-methylpyrrolidone, N-ethyl-2-pyrrolidone, N,N'-dimethylacetamide, diethylene glycol dimethyl ether , cyclopentanone, γ-butyrolactone, α-ethinyl-γ-butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, N-cyclohexyl-2-pyrrolidone , dimethyl hydrazine, hexamethyl phosphoniumamine, pyridine, γ-butyrolactone, diethylene glycol monomethyl ether. These may be used alone or in combination of two or more. The amount of the solvent to be used is not particularly limited. For example, the coating film thickness or viscosity may be used in an amount of 50 to 9000 parts by mass based on 100 parts by mass of the (A) polyphthalate.

In the photosensitive resin composition of the present invention, a sensitizer may be added in order to further improve the light sensitivity. Examples of the sensitizer include michelone, 4,4'-bis(diethylamino)benzophenone, and 2,5-bis(4'-diethylaminobenzylidene). Cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-dimethylaminobenzylidene)-4-methylcyclo Hexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4 '-Bis(diethylamino)chalcone, p-dimethylamino cinnamyl dihydrogen ketone (cinnamylidene) Indanone), p-dimethylamino cinnamyl dihydrogen ketone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylamino Phenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylidene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene Acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-ethylhydrazine -7-dimethylamino coumarin, 3-ethoxycarbonyl-7-dimethylamino coumarin, 3-benzyloxycarbonyl-7-dimethylamino coumarin, 3-methyl Oxycarbonyl-7-diethylamino coumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyl di Ethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-di Methylaminostyryl)benzothiazole, 2-(p-dimethylamine Styryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzimidyl)styrene, etc., from the viewpoint of sensitivity, 4-(1-methylethyl) is used. Preferably, thioxanthone such as -9H-thioxan-9-one is preferred. 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 based on 100 parts by mass of the (A) polyphthalate.

Further, in the photosensitive resin composition of the present invention, in order to improve the adhesion to the substrate, a bonding aid may be added. The auxiliaries can then be used without departing from the spirit of the invention. For example, γ-aminopropyl dimethoxydecane, N-(β-aminoethyl)-γ-aminopropylmethyl group Dimethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-mercaptopropylmethyldimethoxydecane, N-[3-(triethoxycarbenyl) A reaction product of propyl] o-amine phthalamic acid, benzophenone tetracarboxylic dianhydride and (triethoxymethane alkyl) propylamine. The amount of the auxiliary agent is preferably in the range of 0.5 to 10 parts by mass based on 100 parts by mass of the (A) polyphthalate.

Further, a base multiplying agent can be added to the photosensitive resin composition of the present invention. When a thick film pattern is formed, it is necessary to have the same degree of decomposition rate of the photobase generator from the surface to the lower side. At this time, in order to improve the sensitivity, it is preferred to add a base multiplying agent. A base multiplying agent disclosed in, for example, JP-A-2012-237776, JP-A-2006-282657, and the like can be used.

Further, in the photosensitive resin composition of the present invention, other photosensitive components which generate an acid due to light may be added in a range which does not greatly impair the film properties after curing. When a compound having one or two 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 or various functional properties to the photosensitive resin composition of the present invention, various organic or inorganic low molecular or high molecular compounds may be blended. For example, a dye, a surfactant, a flat agent, a plasticizer, fine particles, or the like can be used. The fine particles may contain organic fine particles such as polystyrene or polytetrafluoroethylene, inorganic fine particles such as cerium sol, carbon, or layered silicate, and the like may be porous or hollow. In order to obtain a specific material of a porous shape or a hollow structure, for example, various pigments, Fillers, fibers, etc.

The dry film of the present invention has a resin layer obtained by applying the photosensitive resin composition of the present invention to a carrier film (support) and drying it. The formation of a dry film is carried out by diluting the photosensitive resin composition of the present invention to an appropriate viscosity with the above-mentioned organic solvent, and then using a notch wheel coater, a knife coater, a lip coater, a rod coater, An extrusion coater, a reverse roll coater, a transfer roll coater, a gravure coater, a spray coater, or the like is applied to a carrier film to have a uniform thickness. Then, the photosensitive resin composition after coating 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 is generally suitably selected in the range of 10 to 150 μm, preferably 20 to 60 μm after drying.

The carrier film may be a plastic film, preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film or the like. film. The thickness of the carrier film is not particularly limited, and is generally suitably selected in the range of 10 to 150 μm.

After the resin layer formed of the photosensitive resin composition of the present invention is formed on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the film in order to avoid adhesion of dust or the like to the surface of the film. 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. When the cover film is peeled off, the adhesion of the resin layer to the carrier film is small.

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

First, in step 1, a photosensitive resin composition is applied onto a substrate, and a coating film is obtained by drying. A method of applying a photosensitive resin composition to a substrate can be carried out by a conventional method for applying a photosensitive resin composition, for example, a spin coater, a coating bar, a knife coater, or a curtain coating. A coating method such as a curtain coater or a screen printing machine, a method of spray coating by a spray coater, an inkjet method, and the like. The drying method of the coating film can be carried out by air drying, drying by heating in an oven or a hot plate, vacuum drying, or the like. Further, it is preferred that the drying of the coating film is carried out under conditions in which the (A) polyphthalamide is not produced by imidization in the photosensitive resin composition. Specifically, natural drying, air drying, or heat drying can be carried out at 20 to 140 ° C for 1 minute to 1 hour. It is preferred to dry on a hot plate for 1 to 20 minutes. Further, it may be dried in a vacuum, and in this case, it may be carried out at room temperature for 1 minute to 1 hour.

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

Moreover, it can be widely applied to members and materials for high-temperature treatment of substrates such as printed circuit boards because of imidization at low temperatures.

Next, step 2: the above coating film is placed between the masks having the pattern, or directly exposed. The exposure light is used to activate (B) a photobase generator to generate a wavelength of a base. As described above, when a sensitizer is suitably used, the light sensitivity can be modulated. As an exposure device, a contact aligner, a mirror projection, a stepper, and a laser can be used. Direct exposure device, etc.

Next, step 3: heating by promoting the imidization of the coating film by the alkali generated in the coating film. Thereby, in the above step 2, the alkali generated in the exposed portion serves as a catalyst, and (A) the polyphthalate is partially imidized. The heating time and the heating temperature are appropriately changed depending on the type of (A) polyphthalate, the coating film thickness, and (B) the photobase generator. Typically, the coating film thickness of about 10 μm is about 2 to 10 minutes at 110 to 200 °C. When the heating temperature is too low, local oxime imidization cannot be effectively achieved. Further, when the heating temperature is too high, the unexposed portion is imidized, and the solubility of the exposed portion and the unexposed portion is inferior, and there is a concern that the pattern is formed.

Next, step 4: treating the coating film with a developing solution. Thereby, a patterned film of (A) polyphthalate and a partially quinned imidized polyimide can be formed on the substrate.

The method for development may be selected from a conventional development method of a photoresist, such as a rotary spray method, a paddle method, or a dipping method accompanying ultrasonic treatment. Examples of the developer include inorganic bases such as sodium hydroxide, sodium carbonate, sodium citrate, and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine, and triethanolamine, tetramethylammonium hydroxide, and hydrogen hydroxide. An aqueous solution of a quaternary ammonium salt such as tetrabutylammonium. Further, if necessary, an aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol, ethanol or isopropyl alcohol or a surfactant is added may be used. Then, if necessary, the coating film is washed by a cleaning liquid to obtain a pattern film. The washing liquid may be distilled water, methanol, ethanol, isopropanol or the like, alone or in combination. Further, for the developer, for example, N-methyl-2-pyrrolidine can be used. Ketone, N-ethinyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl hydrazine, γ-butyrolactone, hexamethylphosphorus Tridecylamine, methanol, ethanol, isopropanol, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3 An organic solvent such as methoxypropionate, ethyl-3-ethoxypropionate, 2-heptanone, ethyl acetate or diacetone alcohol.

Then, step 5: heating the pattern film. The heating temperature can be suitably set to harden the patterned film of polyimine. For example, in an inert gas, heat at 150 to 300 ° C for about 5 to 120 minutes. The preferred range of heating temperature is 150 to 250 ° C, and the preferred range is 180 to 220 ° C. Heating is performed, for example, by using a hot plate, an oven, and a temperature-programmable oven. In this case, air (air) may be used, or an inert gas such as nitrogen or argon may be used.

The use of the photosensitive resin composition of the present invention is not particularly limited, and examples thereof include printing inks, adhesives, fillers, electronic materials, optical circuit parts, molding materials, resist materials, building materials, ternary shapes, optical members, and the like. , the various fields used in the use of resin materials. Products, etc. In particular, it is suitable for a wide range of fields in which the properties of the polyimide film are excellent in heat resistance, dimensional stability, and insulation properties. Products such as paints or printing inks, or color filters, flexible films for displays, semiconductor devices, electronic parts, interlayer insulating films, solder resists, etc., wiring films, optical circuits, optical circuit parts, anti-reflection The use of films, holograms, optical components or building materials.

In particular, the sensitization of the present invention containing (A) polyphthalate The resin composition is mainly used as a pattern forming material (resistance), whereby the patterned film is formed as a permanent film made of polyimide, and functions to impart heat resistance or insulation properties. For example, it can be applied to a wiring film, a tin bank, an optical circuit, an optical circuit component, or the like, which is a color filter, a flexible display film, an electronic component, a semiconductor device, an interlayer insulating film, a solder resist, or a cover film. Antireflective film, other optical components or electronic components.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In addition, in the following, when "parts" and "%" are not specifically stated, they are all quality standards.

[Synthesis Example 1: Synthesis of Polyurethane A-1]

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

Three-necked flask of 100ml in capacity, into an acid anhydride half esters described in the table and anhydrous 5mmol 3- methyl-1-phenyl-2-phospholene post-ene (phosphorene) 1- oxide 0.0125 mmol, nitrogen flow 10 ml of the dehydrated guanidine was dissolved. 5 mmol of anhydrous ITI (isophorone diisocyanate) as a diisocyanate was dissolved in 5 ml of dehydrated cyclobutyl hydrazine, and dropped into the flask over about 5 minutes. The mixed solution was allowed to react at 200 ° C for 3 hours, and precipitated in 500 ml of MeOH. The solution containing the precipitate was filtered and dried to obtain a polymer precursor polymer. The resulting polymer was dissolved in DMAc (N,N-dimethylacetamide) and reprecipitated with MeOH. Filtration and drying were carried out to prepare a 15% by mass polyglycolate A-1 solution using dehydrated DMAc as a solvent.

[Synthesis Example 2: Synthesis of Polyurethane A-2]

A polyphthalate A-2 solution was prepared in the same manner as in Synthesis Example 1, except that 6FDA which is an acid dianhydride was changed to PMDA (pyromellitic anhydride).

[Synthesis Example 3: Synthesis of Polyurethane A-3]

A polyperurate A- was produced in the same manner as in Synthesis Example 1, except that the anhydrous ITI as a diisocyanate was changed to anhydrous MDI (methylene diphenyl 4,4'-diisocyanate) described in the following Table. 3 solution.

[Synthesis Example 4: Synthesis of Polyamine A-4]

The polyphthalate A-4 solution was prepared in the same manner as in Synthesis Example 1, except that the 6FDA as the acid dianhydride was changed to PMDA, and the anhydrous ITI as the diisocyanate was changed to the anhydrous MDI described in the following Table.

[Synthesis Example 5: Synthesis of Polyurethane A-5]

A polyphthalate A-5 solution was prepared in the same manner as in Synthesis Example 1, except that the anhydrous ITI as the diisocyanate was changed to the anhydrous TDI-1 (2,4-toluene diisocyanate) described in the following Table.

[Synthesis Example 6: Synthesis of Polyurethane A-6]

A polyphthalate A-6 solution was prepared in the same manner as in Synthesis Example 1, except that the 6FDA as the acid dianhydride was changed to PMDA, and the anhydrous ITI as the diisocyanate was changed to the anhydrous TDI-1 described in the following Table.

[Synthesis Example 7: Synthesis of Polyurethane A-7]

In addition to changing the 6FDA as an acid dianhydride to TDA (1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)naphthalene [1,2- c] furan-1,3-dione), the anhydrous ITI as a diisocyanate was changed to the anhydrous TDI-2 (mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate described in the following table ( Polyacetate A-7 solution was prepared in the same manner as in Synthesis Example 1 except for 80:20.

[Synthesis Example 8: Synthesis of polyphthalate A-8]

A polyphthalate A-8 solution was prepared in the same manner as in Synthesis Example 1, except that the 6FDA as the acid dianhydride was changed to TDA, and the anhydrous ITI as the diisocyanate was changed to the anhydrous MDI described in the following table.

[Synthesis Example 9: Synthesis of Polyurethane A-9]

In addition to changing the 6FDA as acid dianhydride to TDA, and synthesis Example 1 A polyphthalate A-9 solution was also prepared.

[Synthesis Example 10: Synthesis of Polyurethane A-10]

In the same manner as in Synthesis Example 1, except that the 6 FDA as the acid dianhydride was changed to PMDA, and the anhydrous ITI as the diisocyanate was changed to the anhydrous HMDI (hexamethylene diisocyanate) described in the following Table. A-10 solution.

[Synthesis Example 11: Synthesis of polyphthalate A-11]

A polyphthalate A-11 solution was prepared in the same manner as in Synthesis Example 1, except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 12: Synthesis of Polyurethane A-12]

A polyphthalate A-12 solution was prepared in the same manner as in Synthesis Example 2 except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 13: Synthesis of Polyurethane A-13]

A polyphthalate A-13 solution was prepared in the same manner as in Synthesis Example 3 except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 14: Synthesis of Polyurethane A-14]

A polyphthalate A-14 solution was prepared in the same manner as in Synthesis Example 4 except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 15: Synthesis of Polyurethane A-15]

A polyphthalate A-15 solution was prepared in the same manner as in Synthesis Example 5 except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 16: Synthesis of Polyurethane A-16]

A polyphthalate A-16 solution was prepared in the same manner as in Synthesis Example 6, except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 17: Synthesis of Polyurethane A-17]

A polyphthalate A-17 solution was prepared in the same manner as in Synthesis Example 7, except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 18: Synthesis of Polyurethane A-18]

A polyphthalate A-18 solution was prepared in the same manner as in Synthesis Example 8, except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 19: Synthesis of Polyurethane A-19]

A polyphthalate A-19 solution was prepared in the same manner as in Synthesis Example 9, except that in MeOH, MeOH was changed to tert-butanol.

[Synthesis Example 20: Synthesis of Polyurethane A-20]

A polyphthalate A-20 solution was prepared in the same manner as in Synthesis Example 10 except that in MeOH, MeOH was changed to tert-butanol.

[Comparative Synthesis Example 1: Synthesis of Polylysine R-1]

In a separable flask having a capacity of 300 ml, 30 mmol of the diamine described in the following table was charged, and then the diamine was dissolved by dehydrating DMAc (N,N-dimethylacetamide) under a nitrogen stream. After all the diamine was dissolved, 6 FDA 30 mmol described in the following table as an acid anhydride was slowly added. After 6 FDA adhering to the wall of the flask was poured into the reaction solution with a small amount of DMAc, the mixture was stirred at room temperature for 24 hours to obtain a 15 mass% polyamine acid solution. The amount of the dehydrated DMAc charged was 75% by mass based on the amount of the polyamic acid solution.

[Comparative Synthesis Example 2: Synthesis of Polylysine R-2]

A poly-proline R-2 solution was prepared in the same manner as in Comparative Synthesis Example 1, except that 6FDA as an acid anhydride was changed to PMDA.

[Comparative Synthesis Example 3]

According to the synthesis procedure described in Comparative Example 2 of JP-A-2003-084435, 3,3',4,4'-diphenylether tetracarboxylic dianhydride (ODPA), 4,4'-diamine is used. Polydidecylate R-3 solution was prepared by synthesizing 100% esterified polyphthalate by using diphenyl ether (DDE, ODA) and ethanol (EtOH).

(Examples 1 to 28, Comparative Examples 1 to 3)

With the blending ratio (mass ratio) described in the following Tables 23 and 24, a photobase generator was prepared with respect to the polyphthalate or polylysine solution obtained above, and the photosensitivity of the examples and the comparative examples was obtained by dissolution. Resin composition. The photobase generator was added in an amount of 10% by mass based on the total amount of the photosensitive resin composition. Further, the amount of the polyamidomate and the polyaminic acid in the table indicates the amount of the solid component.

[Formation method of pattern film]

Each of the photosensitive resin compositions of the examples and the comparative examples was spin-coated on a wafer, and dried on a hot plate at 80 ° C for 20 minutes to have a film thickness after drying of 5 μm. A pattern mask was placed on the obtained dried film, and a broad exposure was performed using the exposure amount described in Tables 23 and 24 using a desktop exposure apparatus (manufactured by Sanyo Electric Co., Ltd.). The wafer was heated on a hot plate at 150 ° C for 6 minutes, and then immersed in an organic solvent developing solution (DMAc (dimethylacetamide)) or an alkali developing solution (2.38 mass% TMAH (tetramethylammonium hydroxide) Development was carried out in a mixed solution of an aqueous solution and 2-propanol in a 1:1 weight ratio.

[Evaluation of resolution]

The evaluation of the resolution was performed by observing the pattern after development by an electron microscope, and the size of the smallest shape which was well analyzed in the pattern formation was evaluated.

Value: Minimum graphic size (μm)

×: Cannot form a pattern

From the results shown in Tables 23 and 24, it was found that the photosensitive resin composition of the present invention can obtain a pattern film. Further, compared with the nonionic photobase generator, the composition containing the ionic photobase generator has a higher sensitivity and a better resolution. In addition, by using poly-telluric acid Tert-butyl ester, Alkaline development has a promoting effect on the dissolution of the unexposed portion, and a better pattern can be formed. Further, in place of the specific polyphthalate ester of the present invention, the photosensitive resin composition of the comparative example in which another polyglycolic acid or polyglycolate is blended is difficult to form.

Claims (7)

A photosensitive resin composition comprising (A) a polyphthalate and (B) a photobase generator, wherein the (A) polyphthalamide has the following formula ( 1) the structure of the representation, (In the formula (1), R ₁ is a tetravalent organic group, and R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded by an alkyl group, and an alkyl group. Any one, X is a divalent organic group, and R ₃ and R ₄ are a monovalent organic group which may be the same or different from each other or a functional group having a fluorene, m is an integer of 1 or more, and n is an integer of 0 or more) . The photosensitive resin composition of the first aspect of the invention, wherein R ₁ in the above formula (1) is a tetravalent organic group containing a condensed ring of an aromatic ring and an aliphatic hydrocarbon ring, and contains an aromatic group and a fat. a tetravalent organic group of a cyclic hydrocarbon group or a tetravalent organic group of a fluorine atom. The photosensitive resin composition of the first aspect of the invention, wherein the (A) polyphthalate is a structure having at least one of the following general formulae (1-1) and (1-2), (In the formula (1-1), R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded to an alkyl group, and an alkyl group, and X is 2 a valence organic group, R ₃ and R ₄ are a monovalent organic group which may be the same or different from each other or a functional group having a fluorene, m is an integer of 1 or more, and n is an integer of 0 or more) (In the formula (1-2), R ₂ is a group having an alicyclic skeleton, a phenyl group, a group having a stretching diphenyl skeleton bonded to an alkyl group, and an alkyl group, and X is 2 The valence organic group, R ₃ and R ₄ are a monovalent organic group or a functional group having a fluorene which may be the same or different from each other, m is an integer of 1 or more, and n is an integer of 0 or more). The photosensitive resin composition of claim 1, wherein the (B) photobase generator is an ionic photobase generator. A dry film obtained by applying a photosensitive resin composition according to claim 1 of the patent application to a film and drying the resin layer. A cured product obtained by hardening a photosensitive resin composition according to any one of claims 1 to 4 or a resin layer of a dry film according to claim 5 of the patent application. A printed circuit board having a cured product as in claim 6 of the patent application.