KR20170017999A - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

A curable resin composition, a dry film, a cured product and a printed wiring board excellent in resolution, toughness and heat resistance are provided. (A) an amide imide resin having at least one structure represented by the following formula (1) or (2) and an alkali-soluble functional group, (B) an inorganic particle having an average particle diameter of 200 nm or less, (C) (D) a compound having an unsaturated double bond. (B) The inorganic particles having an average particle diameter of 200 nm or less are preferably silica, and it is preferable that the inorganic particles (E) include a thermosetting resin.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board,

The present invention relates to a curable resin composition, a dry film, a cured product, and a printed wiring board, and more particularly, to a curable resin composition, a dry film, a cured product, and a printed product capable of obtaining a cured product having superior resolution, toughness, To a wiring board.

At present, some solder resist compositions for printed wiring boards for civil use and most industrial printed wiring boards are subjected to ultraviolet ray irradiation and development to form an image, and after completion of hardening (final curing) by heat or light irradiation, Based solder resist composition is used. Among these, in consideration of environmental problems, an alkali developing type photo-solder resist composition using an aqueous alkali solution as a developer has become mainstream, and is used in large quantities in the production of actual printed wiring boards.

Conventionally, an alkali-soluble resin, particularly an epoxy acrylate-modified resin, has been generally used for an alkali developing type photo-solder resist composition. For example, Patent Document 1 proposes a solder resist composition comprising a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolac epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, and an epoxy compound.

Japanese Patent Application Laid-Open No. 61-243869

Today, as the curable resin composition, phenol novolak type (cresol novolak type) epoxy acrylate resin or acrylic type copolymerizable resin is widely used as an alkali soluble type. However, the phenol novolak type epoxy acrylate resin is not always excellent in toughness, and the acrylic copolymer type resin is poor in heat resistance. Thus, in the conventional curable resin composition, it has been difficult to highly compatibilize toughness and heat resistance. On the other hand, in mounting a semiconductor package component on a printed wiring board in recent years, the increase in the number of connected I / O and the miniaturization of parts progress simultaneously, and the wiring density is rapidly increasing. In order to enable high-density wiring, a curable resin composition having high resolution is required.

Accordingly, an object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board, which can obtain a cured product having superior resolution, toughness and heat resistance.

The present inventors have intensively studied to solve the above problems and found that the resin used for the curable resin composition is a resin having a specific structure and that the particle diameter of the inorganic particles as fillers is made to be a predetermined value or less, The present invention has been completed.

That is, the curable resin composition of the present invention comprises: (A)

(B) an inorganic particle having an average particle size of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond, wherein the amide-imide resin has at least one structure and an alkali- .

The curable resin composition of the present invention may contain a resin having a structure different from that of the (A) amideimide resin and having an alkali-soluble functional group. The inorganic particles (B) having an average particle diameter of 200 nm or less are preferably silica. Further, it is preferable to include a thermosetting resin (E). Further, the thermosetting resin (E) is preferably an epoxy resin having an alicyclic skeleton.

The dry film of the present invention is characterized in that the curable resin composition of the present invention has a resin layer obtained by applying and drying on a film.

The cured product of the present invention is characterized in that the curable resin composition of the present invention is cured or the resin layer of the dry film of the present invention is cured.

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

According to the present invention, it is possible to provide a curable resin composition, a dry film, a cured product and a printed wiring board which can obtain a cured product excellent in resolution, toughness and heat resistance.

Hereinafter, embodiments of the present invention will be described in detail.

[Curable resin composition]

The curable resin composition of the present invention (hereinafter also referred to as " resin composition ") comprises (A)

(Hereinafter referred to as " component (A) ") having at least one structure represented by the following formula (1) and an alkali-soluble functional group ), A photopolymerization initiator (hereinafter also referred to as "component (C)"), and (D) a compound having an unsaturated double bond (hereinafter also referred to as "component (D)"). By using a resin having the above structure as the resin component of the resin composition and using inorganic particles having an average particle diameter of 200 nm or less as a filler, a cured product having excellent resolution, toughness and heat resistance can be obtained.

Further, the resin composition of the present invention can be developed with a weakly alkaline aqueous solution such as an aqueous solution of sodium carbonate, an aqueous solution of potassium carbonate, or an aqueous solution of ammonia, so that it is not necessary to use a strong alkaline developer when developing. Further, since the development can be performed with a weakly alkaline aqueous solution, the environmental load is small. The resin composition of the present invention has a solubility of 0.05 g / L or more in 1 minute, for example, in an aqueous solution of sodium carbonate (30 DEG C, 1 mass%).

Hereinafter, each component of the resin composition of the present invention will be described in detail.

≪ Component (A) >

The component (A) of the resin composition of the present invention is a compound represented by the following formula (1) or (2)

And an amide imide resin having an alkali-soluble functional group. When the resin composition of the present invention contains a resin having an imide bond directly bonded to a cyclohexane ring or a benzene ring, a cured product excellent in toughness and heat resistance can be obtained. In particular, the amide imide resin having the structure represented by the formula (1) has excellent light transmittance, so that the resolution of the resin composition can be improved. In the resin composition of the present invention, the component (A) preferably has transparency. For example, the transmittance of light having a wavelength of 365 nm is preferably 70% or more at 25 占 퐉 of the dried coating film of the component (A).

The content of the structures of the formulas (1) and (2) in the component (A) of the resin composition of the present invention is preferably from 10 to 70 mass%. By using such a resin, a cured product excellent in solvent solubility and excellent in heat resistance, physical properties such as tensile strength and elongation, and dimensional stability can be obtained. , Preferably 10 to 60 mass%, and more preferably 20 to 50 mass%.

As the amide imide resin having a structure represented by the formula (1), particularly preferable is an amide imide resin represented by the formula (3A) or (3B)

(Wherein R is a monovalent organic group and is preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group and is a direct bond, CH ₂ or C ( CH ₃ ) ₂ ) is preferable because it is excellent in physical properties such as tensile strength and elongation and dimensional stability. In the resin composition of the present invention, from the viewpoints of solubility and mechanical properties, resins having the structures of the formulas (3A) and (3B) in an amount of 10 to 100 mass% can be suitably used as the component (A). And more preferably 20 to 80 mass%.

In the resin composition of the present invention, as the component (A), an amideimide resin containing 5 to 100 mol% of the structures of the formulas (3A) and (3B) can be preferably used from the viewpoints of solubility and mechanical properties. , More preferably 5 to 98 mol%, still more preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.

As the amide imide resin having a structure represented by the formula (2), particularly preferred is an amide imide resin represented by the formula (4A) or (4B)

(In the formulas (4A) and (4B), R is a monovalent organic group and is preferably H, CF ₃ or CH ₃ , and X is a direct bond or a divalent organic group and is a direct bond, CH ₂ or C CH ₃ ) ₂ ) is preferable because a cured product having excellent mechanical properties such as tensile strength and elongation can be obtained. In the resin composition of the present invention, from the viewpoints of solubility and mechanical properties, resins having 10 to 100 mass% of the structures of the formulas (4A) and (4B) as the component (A) can be suitably used. And more preferably 20 to 80 mass%.

Amide imide resins containing 2 to 95 mol% of the structures of the formulas (4A) and (4B) as the component (A) in the composition of the present invention can also be preferably used for the reasons of exhibiting good mechanical properties. And more preferably 10 to 80 mol%.

The component (A) can be obtained by a known method. (1) can be obtained, for example, by using a diisocyanate compound having a biphenyl skeleton and a cyclohexanecarboxylic acid anhydride.

Examples of the diisocyanate compound having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-3,3'-diethyl- Diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1 ' -Biphenyl, 4,4'-diisocyanate-3,3'-ditrifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-ditrifluoromethyl- 1,1'-biphenyl and the like. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate and the like may be used.

Examples of the cyclohexanecarboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and cyclohexanetetracarboxylic acid anhydride.

The amide imide resin having the structure (2) can be obtained, for example, by using a diisocyanate compound having the biphenyl skeleton and a polycarboxylic acid anhydride having two acid anhydride groups.

Examples of polycarboxylic acid anhydrides having two acid anhydride groups include pyromellitic dianhydride, benzophenone-3,3 ', 4,4'-tetracarboxylic dianhydride, diphenyl ether-3,3' Tetracarboxylic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, biphenyl- Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2- (3,4-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, ethylene glycol bisanhydride And alkylene glycol bisanhydrotrimellitate such as trimellitate. Can.

The component (A) of the resin composition of the present invention has, in addition to the structures of the above formulas (1) and (2), an alkali-soluble functional group. By having an alkali-soluble functional group, a resin composition capable of alkali development is obtained. The alkali-soluble functional group includes a carboxyl group, a phenolic hydroxyl group, a sulfo group and the like, and preferably contains a carboxyl group.

The acid value of the component (A) of the resin composition of the present invention is preferably in the range of 20 to 120 mgKOH / g, and more preferably in the range of 30 to 100 mgKOH / g. By setting the acid value of the component (A) within the above range, alkali development can be performed favorably, and a pattern of a normal cured product can be formed. The weight average molecular weight of the component (A) of the resin composition of the present invention varies depending on the resin skeleton, but is preferably 2,000 to 150,000 in general. When the weight-average molecular weight is 2,000 or more, favorable drying properties of the dried coating film, moisture resistance and resolution of the coated film after exposure are good. On the other hand, when the weight average molecular weight is 150,000 or less, development and storage stability are good. More preferably from 5,000 to 100,000.

Specific examples of the component (A) include UNIDIC V-8000 series manufactured by DIC Corporation and SOXR-U manufactured by Nippon Kodoshi Co., Ltd.

The resin composition of the present invention may contain a resin which is different in structure from the component (A) and has an alkali-soluble functional group (hereinafter also referred to as a component (A1)). By containing the component (A1), a dry film having good adhesion between the resin layer and the substrate can be obtained. Therefore, the workability of the dry film is excellent. (A) is different from the structure means that it does not include the structures of the formulas (1) and (2). The alkali-soluble functional group of the component (A1) is the same as the alkali-soluble functional group of the component (A). Examples of the component (A1) include a resin containing a carboxyl group as an starting material of an epoxy resin, a carboxyl group-containing resin having a urethane skeleton (also referred to as a carboxyl group-containing urethane resin), a carboxyl group-containing resin having a copolymerization structure of an unsaturated carboxylic acid, Containing resin comprising a carboxyl group-containing resin as a raw material and a carboxyl group-containing resin obtained by adding a compound having one epoxy group and at least one (meth) acryloyl group in the molecule to the carboxyl group-containing resin. Specific examples of the component (A1) are shown below.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene,? -Methylstyrene, lower alkyl (meth) acrylate or isobutylene.

(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid, and a polycarbonate polyol, a polyether polyol Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(3) A process for producing a polyisocyanate compound, which comprises reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether- A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a heavier reaction of a diol compound such as an A-alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group.

(4) a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a beccylenol type epoxy resin and a biphenol type epoxy resin (Meth) acrylate or a partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(5) In the synthesis of the resin of the above-mentioned (2) or (4), a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) (Meth) acrylated carboxyl group-containing photosensitive urethane resin.

(6) In the synthesis of the resin of the above-mentioned (2) or (4), one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acrylate obtained by adding a compound having a carboxyl group to a terminal (meth) acrylate.

(7) reacting a bifunctional or higher polyfunctional epoxy resin as described below with (meth) acrylic acid to cause addition of a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the hydroxyl groups present in the side chain By weight of a carboxyl group-containing photosensitive resin. Here, the epoxy resin is preferably solid.

(8) a carboxyl group-containing photosensitive resin in which a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional epoxy resin as described below with epichlorohydrin is reacted with (meth) acrylic acid and a dibasic acid anhydride is added to the generated hydroxyl group . Here, the epoxy resin is preferably solid.

(9) A process for producing a polyfunctional phenol compound, such as novolac, which comprises adding a cyclic ether such as ethylene oxide or a cyclic carbonate such as propylene carbonate to a polyfunctional phenol compound to partially esterify the obtained hydroxyl group with (meth) acrylic acid, By weight of a carboxyl group-containing photosensitive resin.

(10) A process for producing a resin composition comprising adding to a resin of the above (1) to (9) one epoxy group in a molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl (meth) A photoacid generator, and a photoacid generator.

The component (A1) may be used without being limited to these components, and a plurality of components may be used in combination. Further, (meth) acrylate is generically referred to as acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions below.

The acid value and the weight average molecular weight of the component (A1) are the same as the acid value and the weight average molecular weight of the component (A). The blending amount of the component (A1) is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 30% by mass or less, based on 100 parts by mass of the total of the components (A) and (A1). By setting the content in the above-described range, a cured product having good toughness and heat resistance can be obtained.

≪ Component (B) >

The resin composition of the present invention (B) includes inorganic particles having an average particle diameter of 200 nm or less. The average particle diameter of the inorganic particles (B) is preferably 150 nm or less, more preferably 100 nm or less. The reason why the average particle size of the inorganic particles is 200 nm or less is as follows. That is, ultraviolet light having a wavelength of 450 nm or less is generally used for exposure of the resin composition. In order to improve the resolution of the resin composition, it is necessary to suppress scattering of light, but when light comes into contact with the inorganic particles in the resin composition, light causes scattering. The inventors of the present invention have found that the resolution can be greatly improved by setting the particle size of the inorganic particles to 200 nm or less, which is about half of the wavelength of ultraviolet rays for exposure. Here, the average particle diameter is a value measured by a laser diffraction method. As a measuring apparatus by the laser diffraction method, a Nanotrac wave can be mentioned.

When the average particle size of the inorganic particles in the cured product is measured, the surface of the cured product is first etched by plasma treatment to make the inorganic particles visible, and the inorganic particles are observed with an SEM (scanning electron microscope). In order to obtain the average particle size of the inorganic particles, the average diameter of the inorganic particles may be calculated by measuring the diameter of the inorganic particles observed in the range of 1 탆 ² and performing the operation five times including the other portions. For example, the plasma treatment is performed using a MARCH PLASMA SYSTEM INC AP-1000 as an apparatus, a power of 500 W, a pressure of 300 Torr, a gas of Ar, and a treatment time of 10 minutes.

Examples of the inorganic particles include inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica powder, hydrotalcite, silicate, Can be used. Of these, silica having a small coefficient of linear expansion can be suitably used. These inorganic particles may be used alone or in combination of two or more.

The amount of the component (B) in the resin composition of the present invention is such that the total amount of 100 parts by mass of the component (A) and the component (A1) (100 parts by mass of the component (A) Is preferably 10 to 150 parts by mass, and more preferably 30 to 120 parts by mass. When the amount of the component (B) is 10 parts by mass or more, the effect of reducing the coefficient of linear expansion can be sufficiently obtained. On the other hand, when the amount of the component (B) is 150 parts by mass or less, can do.

In the resin composition of the present invention, silica having a small coefficient of linear expansion can be suitably used as the component (B) as described above. In this case, as the silica, the surface is preferably treated with a silane coupling agent. This is because it is possible to prevent precipitation or flocculation after being dispersed in a liquid, and as a result, storage stability is excellent. Further, even when the resin composition is blended, it can be stably injected without aggregation, and further, the wettability of the resin and the particles of the resulting cured product can be improved.

Examples of the organic group contained in the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, an ureide group, a chloropropyl group, a mercapto group, And the like. The silane coupling agent may be used alone or in combination of two or more.

≪ Component (C) >

The resin composition of the present invention comprises (C) a photopolymerization initiator. Examples of the photopolymerization initiator (C) used as the photopolymerization initiator include oxime ester-based compounds having a structure represented by the general formula (I),? -Aminoacetophenone-based compounds having a structure represented by the general formula (II) , And a titanocene system having a structure represented by the general formula (IV).

In the general formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

The phenyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms and may contain at least one oxygen atom in the alkyl chain. It may also be substituted with one or more hydroxyl groups. As the cycloalkyl group represented by R ¹ and R ² , a cycloalkyl group having 5 to 8 carbon atoms is preferable. As the alkanoyl group represented by R ¹ and R ² , an alkanoyl group having 2 to 20 carbon atoms is preferable. The benzoyl group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and the like.

In the general formula (II), R ³ and R ⁴ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Or two of them may combine to form a cyclic alkyl ether group.

In the general formula (III), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group or an aryl group substituted with a halogen atom, an alkyl group or an alkoxy group, To 20 carbon atoms (provided that both are carbonyl groups having 1 to 20 carbon atoms).

In the formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group or a heterocyclic ring-containing halogenated aryl group.

Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [ -Methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime). As commercial products, CGI-325, Irgacure OXE01, Irgacure OXE02, N-1919 and NCI-831 manufactured by BASF Japan, and the like can be mentioned. A photopolymerization initiator having two oxime ester groups in the molecule or a photopolymerization initiation system having a carbazole structure can be suitably used. Specifically, oxime ester compounds represented by the following general formula (V) can be mentioned.

(Wherein X represents a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, An alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or an alkylamino group having an alkyl group having 1 to 8 carbon atoms) or a naphthyl group Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, An alkyl group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, An alkyl group having 1 to 8 carbon atoms, or an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), anthryl group, pyridyl group, benzofuryl group or benzothienyl group, Ar represents a bond or a , Alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5- Stilbene-diyl, 4,2'-styrene-diyl, and n is an integer of 0 or 1)

Particularly, in the general formula (V), X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, Ar is a bond or phenylene, naphthylene, thiophene or thienylene .

Further, as a preferable carbazole oxime ester compound, a compound represented by the following general formula (VI) may be mentioned.

(Formula (VI) of the R ¹ represents a phenyl group which may be substituted with alkyl group of 1 to 4 carbon atoms, or a nitro group, an alkyl group, a halogen atom or a number of 1 to 4 carbon atoms. R ² is the number of carbon atoms An alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ³ may be connected to an oxygen atom or a sulfur atom , An alkyl group having 1 to 20 carbon atoms which may be substituted with a phenyl group, a benzyl group which may be substituted with an alkoxy group having 1 to 4 carbon atoms, R ⁴ is a nitro group or XC (= O) - X represents an aryl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (VII) Produces)

Specific examples of the α-aminoacetophenone-based photopolymerization initiator include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Irgacure 369, trade name, (1-methyl-1-morpholinoethane (Irgacure 907, trade name, manufactured by BASF Japan) and 2- (dimethylamino) (Irgacure 379, trade name, manufactured by BASF Japan), or a solution thereof can be used.

Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxy Benzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Examples of commercially available products include Lucillin TPO and Irgacure 819 manufactured by BASF.

As the titanocene photopolymerization initiator, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol- . Commercial products include Irgacure 784 manufactured by BASF Japan.

Examples of other photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloro anthraquinone and 2-amylanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; Xanthones; Various peroxides such as 3,3'4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone; 1,7-bis (9-acridinyl) heptane and the like.

In the resin composition of the present invention, in addition to the above-mentioned photopolymerization initiator, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, And tertiary amines such as amines, can be used in combination with one or more of the above-mentioned photo-sensitizers. Further, when a deeper photocuring depth is required, a 3-substituted coumarin dye, a leuco dye or the like may be used in combination as a curing aid, if necessary.

In the resin composition of the present invention, the blending ratio of the component (C) is 100 parts by mass in total (100 parts by mass of the component (A)) when the component (A) Is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, still more preferably 0.1 to 15 parts by mass. By setting the compounding amount of the component (C) within the above range, it is possible to sufficiently generate radicals necessary for the reaction, and light can be transmitted to the core portion, thereby avoiding the problem that the cured product becomes brittle. The component (C) may be used singly or in combination of two or more.

≪ Component (D) >

The resin composition of the present invention contains (D) a compound having an unsaturated double bond. The component (D) is photo-cured by irradiation with an active energy ray to insolubilize or insolubilize the resin composition of the present invention in an aqueous alkali solution. Examples of such compounds include polyester (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, urethane And specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; There may be mentioned polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts or? -Caprolactone adducts Polyfunctional acrylates; Phenoxy acrylate, bisphenol A diacrylate, polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and acrylates and melamine acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene or a polyester polyol, or a urethane acrylate through a diisocyanate, and And at least one kind of each methacrylate corresponding to the acrylate.

In addition, epoxy acrylate resins obtained by reacting acrylic acid with polyfunctional epoxy resins such as cresol novolak type epoxy resins, and epoxy acrylate resins obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate And an epoxy urethane acrylate compound obtained by reacting a half urethane compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition. The above compounds having an ethylenic unsaturated group in the molecule may be used singly or in combination of two or more.

The proportion of the component (D) is preferably from 1 to 60 parts by mass per 100 parts by mass of the total of the components (A) and (A1) (100 parts by mass of the component (A) More preferably 5 to 50 parts by mass, and still more preferably 10 to 40 parts by mass. By setting the amount of the component (D) in the above range, good photoreactivity can be obtained and heat resistance can be obtained.

≪ (E) Thermosetting resin >

The resin composition of the present invention preferably contains a thermosetting resin (E) (hereinafter also referred to as "component (E)") for further improving the heat resistance. As the thermosetting resin, for example, a thermosetting resin such as a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin, etc. may be used in a molecule such as two or more cyclic ether groups and / or cyclic thioether groups, polyisocyanate compounds, and block isocyanate compounds Known thermosetting resins such as compounds having two or more isocyanate groups or blocked isocyanate groups, amine resins such as melamine resin and benzoguanamine resin and derivatives thereof, bismaleimide, oxazine, cyclocarbonate compound and carbodiimide resin .

As the epoxy resin, a known multi-functional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be in the form of a liquid or solid to semi-solid. As the polyfunctional epoxy resin, bisphenol A type epoxy resin; Brominated epoxy resin; Novolak type epoxy resins; Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resins; Hidanto dolphin epoxy resin; Alicyclic epoxy resins; Trihydroxyphenylmethane type epoxy resin; Biscylenol type or biphenol type epoxy resins or mixtures thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resins; Diglycidyl phthalate resin; Tetraglycidylsilanoy ethane resin; A naphthalene group-containing epoxy resin; An epoxy resin having a dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; CTBN-modified epoxy resin, and the like, but are not limited thereto. Examples of the epoxy resin include novolak type epoxy resins of bisphenol A type or bisphenol F type, bisacylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type (biphenylaralkyl type) epoxy resins, naphthalene type epoxy resins Their mixtures are preferred.

Particularly, as the thermosetting resin, an epoxy resin having a naphthalene skeleton is preferable. The reason for this is that naphthalene has a planar structure, which can lower the coefficient of linear expansion and further improve the heat resistance. These thermosetting resins may be used singly or in combination of two or more kinds. Examples of commercial products of epoxy resins having a naphthalene skeleton include ESN-190, ESN-360, EPICLON HP-4032 and EPICLON HP-4032D manufactured by Shinnittsu Kagaku Co.,

As the component (E), it is preferable that the component (E) is colorless from the viewpoint of resolution. As the component (E), a thermosetting resin having an alicyclic skeleton is preferable. For example, a dicyclopentadiene skeleton-containing thermosetting resin is preferable, and a dicyclopentadiene skeleton-containing epoxy resin is particularly preferable. Further, the thermosetting resin having an alicyclic skeleton is preferable because it has an effect of improving the glass transition temperature as compared with the epoxy resin having a chain skeleton.

The mixing ratio of the component (E) is preferably from 10 to 100 parts by mass per 100 parts by mass of the total of the components (A) and (A1) (100 parts by mass of the component (A) , And more preferably 10 to 80 parts by mass. By setting the blending amount of the component (E) within the above range, it is possible to obtain a composition having heat resistance and having both good developability and photoreactivity.

When a thermosetting resin (E) is contained in the resin composition of the present invention, a thermosetting catalyst may be contained. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as nonethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. Further, in addition to these, it is also possible to use at least one compound selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl- S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl- S-triazine derivatives such as cyanuric acid adducts may also be used.

Examples of commercially available thermosetting catalysts include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., U-CAT 3503N, DBT, DBN, U-CATSA102, and U-CAT5002 (both bicyclic amidine compounds and salts thereof), and the like can be given as examples of CAT3502T (all of the block isocyanate compounds of dimethylamine). These may be used singly or in combination of two or more. In the resin composition of the present invention, the blending amount of the thermosetting catalyst is such that the total amount of 100 parts by mass of the component (A) and the component (A1) (100 parts by mass of the component (A) , Preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5.0 parts by mass.

Further, the resin composition of the present invention can be used for the preparation of a composition or for adjusting the viscosity for application to a substrate or a carrier film. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents may be used alone or in combination of two or more.

<Others>

(A) an amide imide resin having at least one structure represented by the above formula (1) or (2) and an alkali-soluble functional group, (B) an inorganic particle having an average particle diameter of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond. The other components are not particularly limited. For example, in the resin composition of the present invention, if necessary, a coloring agent (for example, a white coloring agent such as titanium oxide, carbon black, a black coloring agent such as titanium black, phthalocyanine blue, phthalocyanine green, disazo yellow Etc.), thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents and the like.

The resin composition of the present invention is suitable for forming an insulating cured coating of a printed wiring board and is more suitable for forming an insulating permanent coating and is most suitable for forming a coverlay, a solder resist, and an interlayer insulating material. The resin composition of the present invention can also be used for forming solder dams and the like. The resin composition of the present invention may be in the form of a liquid or a dry film obtained by drying the liquid resin composition. The liquid type resin composition may be of a two-part type or the like in terms of storage stability, but may also be of a one-part type.

[Dry Film]

The dry film of the present invention has a resin layer obtained by coating the resin composition of the present invention on a film (hereinafter also referred to as a &quot; carrier film &quot;) and then drying it. The dry film of the present invention can be produced by diluting the resin composition of the present invention with an organic solvent and adjusting the viscosity to an appropriate viscosity and then subjecting the dried film to heat treatment such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Or the like, to a uniform thickness on the carrier film, and drying it at a temperature of usually 50 to 130 ° C for 1 to 30 minutes. The thickness of the coating film is not particularly limited, but may be suitably set in the range of 5 to 150 占 퐉, preferably 10 to 60 占 퐉, as a film thickness after drying. The film is not limited to the carrier film, but may be a cover film.

As the carrier film, a plastic film can be suitably used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

A cover film that can be peeled off may be further laminated on the surface of the film for the purpose of preventing the adhesion of dust to the surface of the film after the resin composition of the present invention is coated on the carrier film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. When peeling the cover film, the film and the cover film The adhesive force of the adhesive agent may be smaller.

The volatile drying that is performed after coating the resin composition of the present invention on the carrier film can be carried out by a hot air circulating drying furnace, a hot plate, a convection oven (hot air in a dryer, A method of countercurrent contact and a method of spraying onto a support from a nozzle) can be used.

[Cured goods]

The cured product of the present invention is obtained by curing the resin composition of the present invention and curing the resin layer of the dry film of the present invention. The cured product of the present invention can be obtained by applying the resin composition of the present invention, volatilizing and drying the solvent, and then exposing the coating film obtained or the dry film by irradiating the active energy ray, Can be obtained by curing the exposed portion.

[Printed circuit board]

The printed wiring board of the present invention comprises the cured product of the present invention. The printed wiring board of the present invention can be obtained by a method of directly applying the curable resin composition of the present invention on a printed wiring board and a method of using the dry film of the present invention.

In the case of producing the printed wiring board of the present invention by a direct application method, the resin composition of the present invention is directly applied on a printed circuit board formed on a circuit to form a coating film of the resin composition, Or selectively irradiating an active energy ray through a patterned photomask to expose the unexposed portion, and developing the unexposed portion with a dilute aqueous alkali solution to form a resist pattern. In addition, a resist pattern is irradiated with an active energy ray, for example, at 500 to 2000 mJ / cm 2, and heated to a temperature of, for example, about 140 to 180 ° C to cure the printed wiring board having a pattern of a cured product. The irradiation of the active energy ray with respect to the resist pattern is carried out in order to substantially completely cure the component (D) which has not reacted with the exposure at the time of forming the image of the resist pattern.

In the case of using a dry film, the dry film of the present invention is bonded to a circuit board formed on a circuit to laminate the resin layers. After the exposure, the carrier film is peeled and developed. Thereafter, the resin layer is irradiated with an active energy ray, and is cured by heating at a temperature of, for example, about 140 to 180 DEG C to produce a printed wiring board having a pattern of a cured product. The pattern formation of the cured coating film may be formed by a photolithography method or by a screen printing method or the like.

As an exposure device used for irradiation of an active energy ray, a device capable of irradiating ultraviolet rays in a range of 350 to 450 nm with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, A direct imaging device such as a direct imaging device that draws an image with an active energy ray directly by CAD data from a computer can also be used. As a light source of the direct imaging apparatus, a mercury short arc lamp, an LED, or a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure dose for forming an image of the resist pattern varies depending on the film thickness and the like, but may be generally within the range of 20 to 1500 mJ / cm 2, preferably 20 to 1200 mJ / cm 2.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be employed. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

Example

Hereinafter, the resin composition of the present invention will be described in detail with reference to Examples.

&Lt; Examples 1 to 25 and Comparative Examples 1 to 3 >

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the blend of Tables 1 to 4 below. The obtained resin composition was applied to the entire surface of the copper foil substrate for pattern evaluation for evaluation by screen printing, dried at 80 DEG C for 30 minutes, and cooled to room temperature. Thereafter, the obtained evaluation substrate was exposed to a resist pattern at an optimum exposure dose using an exposure apparatus equipped with a high-pressure mercury lamp, and developed at a temperature of 30 占 폚 in a 1 mass% sodium carbonate aqueous solution at a spray pressure of 0.2 MPa for 90 seconds. After the formation of the resist pattern of the cured product, ultraviolet rays were irradiated in a UV conveyer under the condition of an integrated exposure dose of 1000 mJ / cm 2, and then cured by heating at 180 캜 for 60 minutes. The amidimide resin (A-1) and the other resins (A1-1) and (A1-2) were synthesized by the following synthesis method. The obtained evaluation substrate was evaluated for resolution, tensile strength, elongation, coefficient of linear expansion, and glass transition point. The average particle size of the inorganic particles in Tables 1 to 4 is a measurement value by laser diffraction method. The optimum exposure dose was obtained by the following procedure.

<Optimum exposure dose>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were prepared according to the blend of Tables 1 to 4 below. Subsequently, the copper-clad laminate substrate was buffed, polished, washed, and dried. The obtained resin composition was applied by screen printing and dried in a hot-air circulation type drying furnace at 80 ° C for 30 minutes. After drying, exposure was performed using a high-pressure mercury lamp exposure apparatus via a photomask (manufactured by Eastman Kodak Co., Ltd., step tablet No. 2). The test was carried out for 60 seconds using a developing solution (1 mass% sodium carbonate aqueous solution at 30 캜) at a spray pressure of 2 kg / cm 2, and the number of remaining coating layers was visually determined. The exposure amount at which the number of stages of the remaining coating film was 10 was set as the appropriate exposure amount.

&Lt; Synthesis of amideimide resin (A-1) (Synthesis Example 1)

To a flask equipped with a stirrer, a thermometer and a condenser were added 848.8 g of GBL (gamma butyrolactone), 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), DMBPDI (4,4'-diisocyanate- (0.225 mol) of TMA (trimellitic anhydride), 67.2 g (0.35 mol) of TMA (anhydrous trimellitic acid) and TMA-H (cyclohexane-1,3,4-tricarboxylic acid -3,4-anhydride) was added thereto, and the mixture was heated to 80 ° C while stirring with stirring. The mixture was melted and reacted at this temperature for 1 hour, and reacted again at 160 ° C , And then reacted at this temperature for 5 hours. The reaction proceeded with the blowing of carbon dioxide gas, and the system became a brown transparent liquid. (Resin composition dissolved in? -Butyrolactone) of polyamide-imide resin (A1) having a resin solid content of 17% at 25 ° C of 7 Pa · s and an acid value of 5.3 (KOH mg / g) . The solid dispersion weight of the resin was 31.2 (KOH mg / g). As a result of measurement of gel permeation chromatography (GPC), the weight average molecular weight was 34,000. The polyamide-imide resin (A-1) is a resin having the structures of the above formulas (1) and (2) and a carboxyl group.

&Lt; Synthesis of other resin (A1-1) (Synthesis Example 2) >

To 600 g of diethylene glycol monoethyl ether acetate was added 1070 g of an orthocresol novolak type epoxy resin (EPICLON N-695 manufactured by DIC, softening point 95 캜, epoxy equivalent 214, average number of functional groups 7.6) (total number of glycidyl groups 5.0 mol) of acrylic acid, 360 g (5.0 mol) of acrylic acid and 1.5 g of hydroquinone were charged and stirred at 100 DEG C to dissolve uniformly. Subsequently, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110 캜 and reacted for 2 hours, then heated to 120 캜 and reacted again for 12 hours. 415 g of an aromatic hydrocarbon (Solvesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were charged into the reaction solution obtained and reacted at 110 DEG C for 4 hours, , A cresol novolak type carboxyl group-containing resin solution having a solid acid value of 89 mgKOH / g and a solid content of 65% was obtained. The obtained resin is referred to as the other resin (A1-1).

&Lt; Synthesis of other resin (A1-2) (Synthesis Example 3) >

119.4 g of a novolak type cresol resin (trade name: "SCORNOL CRG951", OH equivalent: 119.4) (manufactured by Showa Kobunshi Co., Ltd.) was added to an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, 1.19 g of potassium hydroxide and 119.4 g of toluene were charged, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Subsequently, 63.8 g of propylene oxide was slowly added dropwise, and the reaction was carried out at 125 to 132 캜 and 0 to 4.8 kg / cm 2 for 16 hours. Thereafter, the reaction solution was cooled to room temperature. To the reaction solution, 1.56 g of 89% phosphoric acid was added and mixed to neutralize potassium hydroxide to obtain a propylene oxide reaction of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / eq. Solution. It was found that an average of 1.08 mole of alkylene oxide per 1 equivalent of phenolic hydroxyl group was added.

Subsequently, 293.0 g of the alkylene oxide reaction solution of the obtained novolac cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air suction pipe , Air was blown at a rate of 10 ml / min, and the mixture was reacted at 110 ° C for 12 hours while stirring. The water produced by the reaction was 12.6 g of water as an azeotropic mixture with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was replaced by 118.1 g of diethylene glycol monoethyl ether acetate with an evaporator, and the mixture was distilled off to obtain a novolak type acrylate resin solution. Subsequently, 332.5 g of the obtained novolak type acrylate resin solution and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air suction tube, blowing air at a rate of 10 ml / min, 60.8 g of hydrophthalic anhydride was gradually added and the reaction was carried out at 95 to 101 ° C for 6 hours. A resin solution of a carboxyl group-containing photosensitive resin having an acid value of 88 mgKOH / g of solid matter and 71% of nonvolatile matter was obtained. Hereinafter, the obtained resin is referred to as the other resin (A1-2).

<Resolution>

The pattern of the cured coating of the prepared evaluation substrate was observed with a scanning electron microscope (SEM) at 1,000 times, and evaluated according to the following evaluation criteria. The obtained results are shown in Tables 1 to 4.

AA: Line and space less than 10μm can be formed.

A: Line and space can be formed below 15㎛.

B: Line and space can be formed below 25 μm.

C: Line and space 25 μm can not be formed.

<Tensile Strength and Shrinkage (Strength)>

A cured coating (10 mm x 40 mm) obtained by curing the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 under the same conditions as described above was coated on a glass substrate having a thickness of 1 mm / min with Autograph AG-X manufactured by Shimadzu Seisakusho Co., Tensile test was performed at a speed of The obtained results are shown in Tables 1 to 4. When the breaking point stress and elongation are large, the toughness is excellent.

A: Breaking point stress 80N / ㎟ or more / elongation 3% or more

B: Breaking point stress 50N / ㎟ or more and less than 80N / ㎟ / elongation 2% or more and less than 3%

C: Breaking point stress less than 50N / ㎟ / elongation less than 2%

&Lt; Linear expansion coefficient, glass transition point (heat resistance) >

The cured coatings of 3 mm x 10 mm in size obtained by curing the resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 under the same conditions as above were cured at a constant heating rate while applying a load of 10 g with TMA6100 manufactured by Seiko Instruments Inc. A tensile test was conducted in a temperature range of 0 占 폚 to 260 占 폚. The coefficient of linear expansion (CTE) was calculated from the newness of the cured film against temperature. Further, a glass transition point (Tg) was obtained from the inflection point. The obtained results are shown in Tables 1 to 4. When Tg is high and CTE is low, heat resistance is excellent.

A: Tg greater than 180 ° C / CTE less than 40ppm

B: Tg 150 ° C or more and less than 180 ° C / CTE 50ppm or less 40ppm or more

C: Tg Less than 150 占 폚 / CTE 50 ppm or more

<Dry Film Workability>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied to a polyethylene terephthalate (PET) film having a thickness of 38 탆 using an applicator having a gap of 60 탆, dried at 80 캜 for 30 minutes, cooled to room temperature , A dry film having a resin layer was produced. The resin layer on the obtained PET film was cut into a size of 10 cm square and bent so as to form a diagonal line. At the time of bending, it was confirmed whether the resin layer existed as a stable film on PET.

A: Like PET, it is bent and does not peel off from PET.

B: It is not peeled from the PET, but the bent part is cracked.

C: The bent part is split and peeled off from the PET.

<Developability>

The resin compositions of Examples 1 to 25 and Comparative Examples 1 to 3 were applied to a copper foil substrate, and after drying, a dry coating film was formed so that the area of the coating film was 10 cm x 10 cm and the thickness was 50 m. 3 L of 1 mass% sodium hydroxide aqueous solution was added to the beaker, and the mixture was heated to 30 캜 to prepare a developer. Further, the weight of the substrate on which the dry coating film was formed was measured. Then, the substrate was immersed in the developing solution, swirled for one minute, and taken out. Thereafter, the substrate was immediately washed with water, dried and then weighed again. Developability, that is, (weight change of substrate: g) / (volume of developer: L) was calculated and evaluated from the change in weight of the substrate. It can be seen that the higher the development value, the faster the developing speed. Further, in the case of a composition containing a general polyimide resin (TECHMIGHT E2020, manufactured by Air Water Inc.), the developability is 0.01 g / L or less and almost insoluble.

Amide imide resin (A-1): The resin (resin solid content 17%) synthesized in Synthesis Example 1

Amide imide resin (A-2): SOXR-U (resin solid content 20%) (manufactured by Nippon Kodoshi Kogyo Co., Ltd.), which corresponds to the carboxyl group-containing amide imide resin having the structure of the above formula

Other resin (A1-1): The carboxyl group-containing resin (solid content 65%) synthesized in Synthesis Example 2

Other resin (A1-2): The carboxyl group-containing resin (solid content: 71%) synthesized in Synthesis Example 3

Inorganic Particles 1: Silica having an average particle diameter of 100 nm

Inorganic Particles 2: Silica having an average particle diameter of 50 nm

Inorganic Particles 3: Barium sulfate having an average particle diameter of 100 nm

Inorganic Particles 4: Silica having an average particle diameter of 1 탆

Photopolymerization initiator 1: TPO made by BASF

Photopolymerization initiator 2: IRG-369 manufactured by BASF

Photopolymerization initiator 3: IRG-OXE02 manufactured by BASF

Compound 1 having an unsaturated double bond: dipentaerythritol hexaacrylate

Compound 2 having an unsaturated double bond: dicyclopentadiene diacrylate

Thermosetting resin 1: Epoxy resin containing naphthalene skeleton HP4032 (150 eq) (manufactured by DIC)

Thermosetting resin 2: naphthol-modified epoxy resin NC7000 (230 eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting resin 3: biphenylaralkyl type epoxy resin NC3000 (275 eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting resin 4: Dicyclopentadiene skeleton-containing epoxy resin XD-1000 (250 eq) (manufactured by Nippon Kayaku Co., Ltd.)

Thermosetting resin 5: dicyclopentadiene skeletal epoxy resin HP-7200H (280 eq) (manufactured by DIC)

Thermal curing catalyst 1: melamine

Thermal curing catalyst 2: Dicyandiamide

It can be seen from Tables 1 to 4 that the resin composition of the present invention can obtain a cured product having excellent resolution, heat resistance and toughness. Further, it can be seen that the dry film obtained from the resin composition of the present invention has excellent workability.

Claims (10)

(A) a compound represented by the following formula (1), (2)

(B) an inorganic particle having an average particle size of 200 nm or less, (C) a photopolymerization initiator, and (D) a compound having an unsaturated double bond, wherein the amide-imide resin has at least one structure represented by the following formula Wherein the curable resin composition is a curable resin composition. The curable resin composition according to claim 1, which comprises a resin having a structure different from that of the (A) amideimide resin and having an alkali-soluble functional group. The curable resin composition according to claim 1, wherein (B) the inorganic particles having an average particle diameter of 200 nm or less is silica. The curable resin composition according to claim 1, which comprises (E) a thermosetting resin. The curable resin composition according to claim 4, wherein the (E) thermosetting resin is an epoxy resin having an alicyclic skeleton. A dry film comprising a resin layer obtained by applying the curable resin composition according to any one of claims 1 to 5 on a film and drying the film. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5. A cured product obtained by curing a resin layer of the dry film according to claim 6. A printed wiring board comprising the cured product according to claim 7. A printed wiring board comprising the cured product according to claim 8.