KR20140147897A - Photocurable resin composition, printed wiring board, and method for producing photocurable resin composition - Google Patents

Abstract

The present invention provides a photocurable resin composition capable of obtaining a cured product having good resolution even though it contains a plurality of kinds of fillers having different refractive indexes. The present invention relates to a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator and two or more fillers having different refractive indexes, wherein at least one filler among the two or more fillers is blended as a powder and at least one filler In the form of a slurry. The present invention also relates to a photo-curable resin composition.

Description

TECHNICAL FIELD The present invention relates to a photocurable resin composition, a printed wiring board, and a method for producing a photocurable resin composition,

The present invention relates to a photo-curable resin composition, a printed wiring board, and a process for producing a photo-curable resin composition. More specifically, the present invention provides a photo-curable resin composition, A printed wiring board comprising the cured product thereof, and a process for producing the photo-curable resin composition.

In general, in a printed wiring board used in electronic equipment or the like, in order to prevent the solder from adhering to an unnecessary part and to prevent the conductor of the circuit from being corroded by oxidation or moisture, A solder resist is formed in an area excluding the connection hole.

As a method of forming a solder resist of a desired pattern on a substrate, a forming method using a photolithography technique is used. For example, a photosensitive solder resist containing an alkali developing type photocurable resin composition is exposed through a pattern mask, and then subjected to alkali development to obtain a pattern using a difference in solubility in an alkali developer generated in the exposed portion and the non- .

Conventional inorganic fillers and organic fillers have been incorporated in solder resists as one of the means for improving the properties of solder resists, such as curing shrinkage inhibition, heat resistance, adhesion and hardness (see, for example, Patent Documents 1 and 2). Various types of fillers have been proposed. In recent years, with the purpose of improving the workability and high performance of the solder resist accompanying the increase in the density of printed wiring boards accompanied by the thinning and shortening of electronics devices, It is considered to increase the effect of the filler.

Japanese Patent Application Laid-Open No. 2001-053448 Japanese Patent Application Laid-Open No. 2002-236363

However, when a plurality of kinds of fillers are blended in a photosensitive solder resist, good resolution can not be obtained when the refractive indexes of the fillers are different, and fine pattern formation can not be achieved in some cases.

Accordingly, an object of the present invention is to provide a photocurable resin composition which can obtain a cured product having good resolution even though it contains a plurality of kinds of fillers having different refractive indexes, a dry film thereof, a cured product obtained by curing them, And a method for producing the photo-curable resin composition.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the above problems can be solved by using a plurality of kinds of fillers having different refractive indexes in the form of powders and slurries, and have completed the present invention.

That is, the photocurable resin composition of the present invention is a photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, and two or more kinds of fillers having different refractive indices, wherein one or more fillers among the two or more kinds of fillers is a powder And one or more fillers are mixed in a slurry state.

The photo-curing resin composition of the present invention preferably has a particle size distribution D ₅₀ of 3.0 μm or less and a D ₉₀ of 8.0 μm or less.

In the photocurable resin composition of the present invention, it is preferable that at least one filler among the two or more fillers has a refractive index of less than 1.5 or more than 1.7 and is blended in a slurry state.

In the photocurable resin composition of the present invention, it is preferable that at least one filler among the above two or more fillers has a refractive index of 1.5 to 1.7 and is blended in powder form.

In the photo-curable resin composition of the present invention, it is preferable that the carboxyl group-containing resin has an aromatic ring.

The photo-curing resin composition of the present invention preferably contains a carboxyl group-containing resin obtained by using a phenol compound as a starting material.

The photocurable resin composition of the present invention preferably further comprises a photoreactive monomer.

The dry film of the present invention is characterized in that any one of the above-mentioned photo-curing resin compositions is applied on a film and dried.

The printed wiring board of the present invention is characterized by comprising a cured product obtained by curing one of the above-mentioned photo-curable resin compositions or the above-mentioned dry film by at least one of irradiation with active energy ray and heating.

The method for producing a photocurable resin composition of the present invention is characterized by including a step of blending two or more kinds of fillers having different refractive indexes in a slurry state with one or more fillers as a powder and one or more fillers.

According to the present invention, there is provided a photocurable resin composition capable of obtaining a cured product having good resolution even though it contains a plurality of kinds of fillers having different refractive indexes, a dry film thereof, a cured product obtained by curing them, A printed wiring board, and a process for producing the photo-curable resin composition.

1 is a chart showing the particle size distribution of the photocurable resin composition of Example 3 measured by a laser diffraction scattering type particle size particle size distribution analyzer.
Fig. 2 is a chart showing the particle size distribution of the photo-curing resin composition (Comparative Example 2) in which only a filler as a powder is blended by a laser diffraction scattering particle size particle size distribution measuring apparatus.

The photo-curable resin composition of the present invention is a photo-curable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator and two or more kinds of fillers having different refractive indices, wherein at least one filler among the two or more kinds of fillers is compounded into a powder , And one or more fillers are blended in a slurry state. Even when two or more kinds of fillers having different refractive indexes are blended, the transparency of the photo-curing resin composition is improved by blending the filler in a slurry state, and a cured product having good resolution can be obtained. Further, by mixing one or more fillers in powder form without blending all of the fillers in a slurry state, it is possible to suppress the deterioration of the increase of the solvent amount and the dryness, and to secure good workability.

The filler can form an aggregate in the photo-curable resin composition, but the photo-curable resin composition of the present invention has a smaller particle size of the aggregate in the composition than when the filler is blended alone. The photo-curable resin composition of the present invention preferably has a particle size distribution D ₅₀ of 3.0 μm or less, a D ₉₀ of 8.0 μm or less, a D ₅₀ of 1.0 μm or less, and a D ₉₀ of 3.0 μm or less. In the present specification, the particle size when the cumulative percentage from the small particle size is 50% is referred to as the particle size distribution D ₅₀ , and the particle size when the cumulative percentage from the small particle size is 90% is referred to as the particle size distribution D ₉₀ . The particle size distributions D ₅₀ and D ₉₀ can be measured by, for example, laser diffraction scattering method using MT3300EX manufactured by Nikkiso Co., Ltd.

The refractive index of the filler compounded in the slurry state is preferably smaller than 1.5 or larger than 1.7. This is because, when the filler having such a refractive index is blended in a slurry state, better resolution can be obtained. It is considered that such a refractive index tends to cause scattering of light since the refractive index of the resin of the photo-curable resin composition is large and the wettability at the interface between the filler and the resin blended in the powder is insufficient. When the filler having such a refractive index is blended in a slurry state, the wettability of the filler and the resin is improved, and it is considered that the scattering of light can be suppressed and the resolution is improved. On the other hand, the refractive index of the filler blended with the powder is preferably 1.5 to 1.7 in view of obtaining good resolution even when blended with the powder. Further, it is considered that the coating film coated with the photocurable resin composition of the present invention has a uniform reflectivity because of its low reflectance.

[Resin containing a carboxyl group]

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. In particular, a photosensitive resin containing a carboxyl group having an ethylenically unsaturated double bond in a molecule is preferable in view of photocurability and resistance to development. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. In the case of using only a carboxyl group-containing water not having an ethylenically unsaturated double bond, in order to render the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups, that is, a photoreactive monomer, in combination with the molecule described below.

Specific examples of the carboxyl group-containing resin include the following compounds (any of oligomers and polymers).

(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) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols, polyether Based on the weight-average molecular weight of the diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group, Containing urethane resin.

(3) 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.

(4) During the synthesis of the resin of the above (2) or (3), 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.

(5) In the synthesis of the resin of the above-mentioned (2) or (3), it is preferable to use a mixture of isophorone diisocyanate and pentaerythritol triacrylate, such as a molar reaction product of one isocyanate group and one or more (meth) (Meth) acrylate of a carboxyl group-containing photosensitive urethane resin.

(6) A photosensitive resin containing a carboxyl group in which a dibasic acid anhydride is added to a hydroxyl group present in a side chain by reacting a bifunctional or higher polyfunctional (solid) epoxy resin as described below with (meth) acrylic acid.

(7) A carboxyl group-containing photosensitive resin composition obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin as described below with epichlorohydrin to react with (meth) acrylic acid to generate a hydroxyl group and generating a dibasic acid anhydride Suzy.

(8) A dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid is reacted with a bifunctional oxetane resin as described below to give a primary hydroxyl group generated by reacting phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or the like Of a dibasic acid anhydride is added to the polyester resin.

(9) A method of reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

(10) reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a monocarboxylic acid containing an unsaturated group, A photosensitive resin containing a carboxyl group obtained by reacting a reaction product with a polybasic acid anhydride.

(11) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and at least one (meth) acryloyl group in one molecule to the resin of the above (1) to (10).

In the present specification, (meth) acrylate is generically referred to as acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

Since the carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution becomes possible.

The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. On the other hand, when the acid value of the carboxyl group-containing resin is 40 mgKOH / g or more, the alkali development is favorable. On the other hand, when the acid value is 200 mgKOH / g or less, dissolution of the exposed portion by the developer can be suppressed, , It is possible to inhibit dissolution and peeling in a developing solution without distinction between the exposed portion and the unexposed portion, whereby the resist pattern can be satisfactorily drawn.

The weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tackfree performance is good, the humidity resistance of the coated film after exposure is good, the film reduction during development is suppressed, and the decrease in resolution can be suppressed. On the other hand, if the weight average molecular weight is 150,000 or less, the developing property is good and the storage stability is excellent.

The amount of such a carboxyl group-containing resin is suitably in the range of 20 to 60 mass%, preferably 30 to 50 mass%, in the photocurable resin composition. When the blending amount of the carboxyl group-containing resin is 20 mass% or more, the film strength is preferable, which is preferable. On the other hand, when the content is 60% by mass or less, the viscosity of the photo-curing resin composition is not excessively increased and the coatability to the carrier film is improved.

These carboxyl group-containing resins may be used without being limited to those listed above, and they may be used singly or in combination of plural kinds. In particular, a resin having an aromatic ring in the carboxyl group-containing resin is preferred because it has a high refractive index and excellent resolution, and a novolak structure is more preferable because it has not only resolution but also excellent PCT and crack resistance. Among them, the carboxyl group-containing resin synthesized by using the phenolic compound as a starting material in the carboxyl group-containing resins (9) and (10) is excellent in HAST resistance and PCT resistance, , And as a result, it is excellent in crack resistance and can be suitably used. Such a carboxyl group-containing resin may be obtained as a resin having no hydroxyl group. Generally, the presence of a hydroxyl group has excellent characteristics such as improvement of adhesion by hydrogen bonding, but it is known that the moisture resistance is remarkably lowered. Specifically, a phenol resin modified with an alkyloxide is partially acrylated with a phenol novolac resin, and an acid anhydride is introduced to obtain a compound having a double bond equivalent of 300 to 550 and an acid value of 40 to 120 mgKOH / g, Resin can be easily obtained.

[Photopolymerization initiator]

Although the photopolymerization initiator is not particularly limited, it is possible to use at least one photopolymerization initiator selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an? -Aminoacetophenone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator and a titanocene photopolymerization initiator Can be suitably used.

The addition amount of the oxime ester-based initiator is also small, and outgas is suppressed, so that it is effective for the PCT resistance and the crack resistance. The acylphosphine oxide photopolymerization initiator is preferred because it has high deep curing ability because it absorbs at long wavelengths of 400 nm or more. In addition, when an acylphosphine oxide photopolymerization initiator is used in addition to the oxime ester-based initiator, it is particularly preferable because a good resolution property is obtained. The titanocene photopolymerization initiator is preferable because it has a very wide light absorption wavelength range, is excellent in deep portion curability, and has high photoreactivity, so that the amount of exposure required for curing is small and high production is possible.

Examples of the oxime ester-based photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02, AD-1919 and NCI-831 manufactured by BASF Japan. Further, a photopolymerization initiation system having two oxime ester groups in the molecule can be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula can be given.

(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 alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms) 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 alkylamino group having 1 to 8 carbon atoms, an alkylamino 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), an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group, Ar represents a bond, To 10 carbon atoms, such as alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5- -Diyl, 4,2'-styrene-diyl, and n is 0 or an integer of 1)

Particularly, in the above general formula, 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.

As preferable carbazole oxime ester compounds, there may be mentioned compounds which can be represented by the following general formulas.

(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms,

R ² represents 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 represents a benzyl group which may be bonded by an oxygen atom or a sulfur atom, an alkyl group of 1 to 20 carbon atoms which may be substituted with a phenyl group, or a benzyl group which may be substituted with an alkoxy group of 1 to 4 carbon atoms,

R ⁴ represents an acyl group represented by 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, ≪ / RTI >

Other examples include Japanese Patent Application Laid-Open Nos. 2004-359639, 2005-097141, 2005-220097, 2006-160634, 2008-094770 A carbazole oxime ester compound described in Japanese Patent Application Laid-Open No. 2008-509967, Japanese Patent Laid-Open Publication No. 2009-040762, and Japanese Patent Laid-Open No. 2011-80036.

The blending amount of such oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 part by mass or more, the photo-curability on copper is improved, the peeling of the coating film is suppressed, and the coating film characteristics such as chemical resistance are improved. On the other hand, if the amount is 5 parts by mass or less, the light absorption on the surface of the solder resist coating film becomes good and the deep portion hardening property is improved. More preferably 0.5 to 3 parts by mass.

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, N, N-dimethylaminoacetophenone, and the like. Examples of commercially available products include IRGACURE 907, IRGACURE 369, IRGACURE 379 manufactured by BASF Japan.

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

It is preferable that the blending amount of the? -Aminoacetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is 0.01 to 15 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 part by mass or more, the photocurability on copper becomes good, the peeling of the coating film is suppressed, and the coating film properties such as chemical resistance become good. On the other hand, when the amount is less than 15 parts by mass, outgas is reduced, light absorption on the surface of the coating film becomes better, and deep portion curability is improved. More preferably 0.5 to 10 parts by mass.

Specific examples of the titanocene photopolymerization initiator include bis (cyclopentadienyl) -di-phenyl-titanium, bis (cyclopentadienyl) -di-chloro-titanium, bis (cyclopentadienyl) -bis (4,5,6-pentafluorophenyl) titanium, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyrrol-1-yl) phenyl) titanium and the like. Commercial products include Irgacure 784 manufactured by BASF Japan.

The blending amount of the titanocene photopolymerization initiator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 part by mass or more, the photocurability on copper becomes good, the peeling of the coating film is suppressed, and the coating film properties such as chemical resistance become good. On the other hand, if it is less than 15 parts by mass, the amount of light absorption is not excessively increased, and the deep portion curing property is improved. More preferably 0.05 to 10 parts by mass.

In the photocurable resin composition of the present invention, in addition to the photopolymerization initiator, a photoinitiator and a sensitizer may be used. Examples of the photoinitiator and sensitizer that can be suitably used include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds and xanthone compounds .

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like.

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- .

Specific examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloro anthraquinone and the like.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and the like .

Specific examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal, and the like.

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- -Benzoyl-4'-propyldiphenyl sulfide and the like.

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.) in a commercial product, Dialkylaminobenzophenone such as 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (produced by International Bio-Synthesis Co., Ltd.) (Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantucure BEA from International Bio-Synthesis), p-dimethylaminobenzoic acid isoamylethyl ester (Kayacure DMBI ), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), and the like.

Of these, thioxanthone compounds and tertiary amine compounds are preferable. Particularly, it is preferable that a thioxanthone compound is included in view of deep curability. Among them, a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone is preferable Do.

The compounding amount of the thioxantane compound is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the compounding amount of the thioxanthone compound is 20 parts by mass or less, the thick film curing property is improved and the increase in the cost of the product can be suppressed. More preferably 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, Tocumarines are particularly preferred.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because it has low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm and is in the ultraviolet region, it is less colored, and a colored pigment is used as well as a colorless transparent photocurable resin composition, It becomes possible to provide a resist film. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in that it exhibits an excellent increase / decrease effect on laser light having a wavelength of 400 to 410 nm.

The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin. When the compounding amount of the tertiary amine compound is 0.1 part by mass or more, a good increase / decrease effect can be obtained. On the other hand, if the amount is less than 20 parts by mass, the light absorption on the surface of the dried solder resist coating film by the tertiary amine compound does not become much worse and the deep curing property becomes good. More preferably 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiator and sensitizer may be used alone or as a mixture of two or more.

The total amount of the photopolymerization initiator, photoinitiator and sensitizer is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When the amount is 35 parts by mass or less, deterioration of the deep portion curing property due to the light absorption can be suppressed.

[Filler]

In the photocurable resin composition of the present invention, two or more kinds of fillers having different refractive indexes are blended. However, the present inventors have found that when one or more fillers among two or more kinds of fillers are blended into a powder and one or more fillers are blended in a slurry state, The transparency of the resulting resin composition is improved and the resolution is improved. In addition, by mixing a filler having a refractive index of less than 1.5 or more than 1.7, preferably a filler having a refractive index of 1.3 or more and less than 1.5 or 1.7 or more, in a slurry state, a higher resolution can be obtained have. When the amount of the filler to be compounded in the slurry state is increased, the amount of the solvent is increased, drying property is deteriorated and workability is lowered. However, not all the fillers are compounded in the slurry state, Drying and workability can be improved. The refractive index of the filler incorporated into the powder is preferably 1.5 to 1.7, more preferably 1.5 to 1.65 in view of obtaining better resolution. In addition, it is considered that the coating film coated with the photocurable resin composition of the present invention is uniformly dispersed in the filler because of low transmittance.

In the present invention, the powder is not particularly limited as long as the filler is in the form of powder, and any known powder may be used. In the present invention, the primary particle diameter means an average primary particle diameter (D ₅₀ ) and can be measured by a laser diffraction scattering method. Further, the total amount of the filler to be incorporated into the powder is preferably 75% or less, more preferably 0.1 to 60% of the total amount of the total fillers in terms of mass. When the compounding amount of the filler is 75% or less of the total amount of the composition, the viscosity of the insulating composition is not excessively increased, the application and the formability become good, and the cured product becomes less brittle.

The slurry state refers to a state in which the filler is dispersed in a liquid such as water or an organic solvent. Since the filler having a small primary particle diameter tends to flocculate when mixed with a liquid, it is preferable to remove the coarse aggregate by filtration through a filter. In order to remove coarse agglomerates, it is preferable to perform filtration through a filter having a size of 10 탆 or less, and more preferably, filtration through a filter having a size of 5 탆 or less. The amount of the filler in the slurry is preferably 10 to 90%, more preferably 10 to 80%. If it is 10% or more, deterioration of workability due to a decrease in viscosity or the like can be suppressed. When it is 90% or less, dispersion stability as a slurry is not excessively lowered and coagulation is suppressed. It is preferable that the primary particle size of the filler to be mixed with the powder and the filler to be mixed with the slurry state are different from each other, and in this case, the filler can be compounded with a high filler. A filler having a small primary particle diameter is preferable because a filler having a primary particle size of 1 탆 or less is blended in a slurry state in that the filler can be blended at a higher filling rate in view of easy aggregation with the powder. The total amount of the solid content of the filler compounded in the slurry state is preferably 10 to 90%, more preferably 20 to 90%, and still more preferably 40 to 90% of the total solid content of the filler in terms of mass. When the content is 10% or more, the effect of improving the transparency becomes good. When the content is 90% or less, the amount of the solvent in the composition is not excessively increased, and deterioration of drying property and sedimentation of the filler component after storage can be suppressed.

The liquid to be mixed with the filler to make the slurry state is not particularly limited, and examples thereof include water and an aqueous solution, and organic solvents described later.

The method of mixing the filler in the powdery and slurry state is not particularly limited, and it may be in the form of a powder and a slurry when mixed with another component called a carboxyl group-containing resin at the time of mixing before the preliminary mixing.

In the present invention, known fillers and organic fillers may be used as the fillers. Examples of inorganic fillers include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, aluminum hydroxide, , Talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite, boron nitride, A glass powder, a diatomaceous earth, an antimony trioxide, a magnesium oxysulfate, a silica glass powder, a silica glass, a steel ball, a balloon, a glass flake, a glass balloon, silica, steel slag, copper, iron, iron oxide, carbon black, , Hydrated aluminum, hydrated gypsum, alum, and the like. Particularly, silica, barium sulfate, talc, hydrotalcite and the like are preferably used.

Examples of the inorganic filler having a refractive index smaller than 1.5 include silica (refractive index: 1.45), potassium (refractive index: 0.07), and potassium hydrogen carbonate (refractive index: 1.48). (Refractive index: 2.37), zirconium oxide (refractive index: 2.4), alumina (refractive index: 1.76), chromium oxide (refractive index: 2.5), cadmium oxide (refractive index: 2.49), cadmium sulfide (Refractive index: 2.72), copper oxide (refractive index: 2.71), copper sulfide (refractive index: 1.73), and the like have. Examples of inorganic fillers having a refractive index of 1.5 to 1.7 include barium sulfate (refractive index: 1.65), talc (refractive index: 1.54-59), magnesium carbonate (refractive index: 1.57-1.60), clay (refractive index: 1.55-1.57) (Refractive index: 1.65), aluminum hydroxide (refractive index: 1.65), boehmite (refractive index: 1.62-1.65), mica powder (refractive index: 1.59), hydrotalcite 1.57), calcium carbonate (refractive index: 1.58), calcium sulfate (refractive index: 1.59), and potassium carbonate (refractive index: 1.5)

Examples of the organic filler include polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, crosslinked polymethacrylate, crosslinked polymethacrylic acid But are not limited to, butyl, polyimide, polyamide, polyester, polyvinyl chloride, polyvinylidene chloride, polydivinylbenzene, fluororesin, polyphenylene oxide, polyphenylene sulfide, polymethylpentene, urea resin, Nylon resin, polyacetal resin, furan resin, silicone resin, cured epoxy resin, and the like. Particularly preferred are polyethylene, polypropylene, crosslinked polymethyl methacrylate, and crosslinked polymethyl methacrylate.

(Refractive index: 1.49), poly (methyl methacrylate) (refractive index: 1.49), vinyl acetate resin (refractive index: 1.46), silicone resin (refractive index: 1.43), polyacetal Resin (refractive index: 1.48), and polypropylene resin (refractive index: 1.48). As the organic filler having a refractive index higher than 1.7, a resin for a polythiourethane optical material (refractive index: 1.75) and the like can be given. (Refractive index: 1.6), polystyrene (refractive index: 1.6), polyethylene (refractive index: 1.53), vinylidene chloride resin (refractive index: 1.61), poly Carbonate (refractive index: 1.59), and the like.

The refractive index of the filler can be measured by the Becke line method. A method of observing a beak line appearing at the interface between a filler and a submerged solution with a microscope fitted with a diaphragm by placing the filler component in a submerged solution and dropping it on a slide glass and mounting a cover glass. can do.

Further, since the filler can be compounded at a higher charge, if the primary particle diameter of the filler to be mixed in the slurry state is 1 탆 or less, the filler can be blended at a higher charge, which is preferable. The lower limit is preferably 0.005 탆 or more.

Examples of the filler having a primary particle diameter of 1 占 퐉 or less are SO-E1 (primary particle diameter: 0.25 占 퐉), SO-E2 (primary particle diameter: 0.5 占 퐉), SO-E3 B-30 (primary particle diameter: 0.3 占 퐉), B-31 (primary particle diameter: 0.3 占 퐉), B-33 (primary particle diameter: 0.3 占 퐉), BF-10 Barium sulphate such as BF-1 (primary particle diameter: 0.05 탆), BF-20 (primary particle diameter: 0.03 탆) and BF-40 (primary particle diameter: H43 (primary particle diameter: 0.75 占 퐉), H43 (primary particle diameter: 0.75 占 퐉), Higilite H42 (primary particle diameter: DHT-4A (primary particle diameter: 0.4 占 퐉), DHT-4A-2 (primary particle diameter: 0.4 占 퐉) -4H (primary particle diameter: 0.4 占 퐉) and hydrotalcite (all manufactured by Kyowa Chemical Co., Ltd.). Among these, barium sulfate is preferable because of its particularly small particle size and easy agglomeration in the case of powder.

The total amount of the fillers is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass, based on 100 parts by mass of the resin containing a carboxyl group. When the compounding amount of the filler is 500 parts by mass or less, the viscosity of the photo-curable resin composition is not excessively increased, printing properties become good, and the cured product becomes less brittle.

(Photoreactive monomer)

The photocurable resin composition of the present invention preferably contains a photoreactive monomer. The photoreactive monomer is a compound having at least one ethylenic unsaturated group in the molecule. The photoreactive monomer is to assist in the photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

As the photoreactive monomer, a photoreactive monomer for publicly known generations can be used. Examples thereof include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate and epoxy . 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; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates such as water; Polyfunctional acrylates such as phenoxy acrylate, bisphenol A diacrylate and 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 may be exemplified by acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or acrylates and melamine acrylates obtained by urethane acrylating through a diisocyanate , And at least one of the respective methacrylates corresponding to the acrylate.

In addition, epoxy acrylate resins obtained by reacting polyfunctional epoxy resins such as cresol novolak type epoxy resins with acrylic acid, or epoxy acrylate resins obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate with isophorone An epoxy urethane acrylate compound in which a half urethane compound of a diisocyanate such as a diisocyanate is further reacted may be used as a photoreactive monomer. Such an epoxy acrylate resin does not deteriorate the touch dry composition and can improve photo-curability.

The compounding amount of the compound having an ethylenic unsaturated group in the molecule used as the photoreactive monomer is preferably 5 to 100 parts by mass, more preferably 5 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the compounding amount is 5 parts by mass or more, the photo-curable resin composition has good photo-curability. On the other hand, when it is 100 parts by mass or less, the coating film becomes less brittle.

(Thermosetting component)

The photocurable resin composition of the present invention may further contain a thermosetting component for the purpose of improving properties such as heat resistance and insulation reliability. Examples of the thermosetting component include an amino resin, an isocyanate compound, a block isocyanate compound, a maleimide compound, a benzoxazine compound, an oxazoline compound, a carbodiimide compound, a cyclocarbonate compound, a polyfunctional oxetane compound, A thermosetting resin for a known purpose such as a resin can be used.

Examples of the amino resin include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycol uril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be prepared by reacting the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound, and methylol urea compound Is converted into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less is desirable for human body and environment.

Examples of commercially available amino resins include Cymel 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper 266, Copper 267, Copper 238, Copper 1141, Copper Copper 272, Copper Copper 202, 750, copper Mx-032, copper Mx-270, copper Mx-280 (manufactured by Mitsui Cyanamid Co., Ltd.), copper foil 1156, copper 1158, copper 1123, copper 1170, copper 1174, copper UFR 65, copper 300 , Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM , Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.), and the like.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate, and adducts, burettes and isocyanurates of the isocyanate compounds exemplified above.

The blocked isocyanate group contained in the block isocyanate compound is a group in which the isocyanate group is protected by a reaction with the blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to form an isocyanate group.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the blocking agent include isocyanurate type, buret type, and adduct type. The isocyanate compound used for synthesizing the block isocyanate compound includes, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam-based blocking agents such as? -caprolactam,? -flareolactam,? -butyrolactam and? -propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scouring, acetal decyl, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

The block isocyanate compound may be a commercially available one such as Sumidor BL-3175, BL-4165, BL-1100, BL-1265, Des Tire all TPLS-2957, TPLS-2062, TPLS-2078, TPLS- B-815 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), Coronate 2513, Coronate 2520 (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name), Desmodur 2170, Desmodur 2265 (manufactured by Sumitomo Bayer Urethane Co., TPA-B80E, 17B-60PX, and E402-B80T (trade names, manufactured by Asahi Kasei Chemicals Co., Ltd., trade name, product of Mitsui Chemical Industries, Ltd.), B-846, B-870, B- And the like. Further, Sumidur BL-3175 and BL-4265 are obtained by using methylethyloxime as a block agent.

The blending amount of the polyisocyanate compound or the block isocyanate compound is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the blending amount is 1 part by mass or more, sufficient toughness of the coating film can be obtained. On the other hand, when the amount is 100 parts by mass or less, deterioration of storage stability is suppressed.

To the photo-curable resin composition of the present invention, an urethane-forming catalyst may be further added. As the urethanation catalyst, it is preferable to use at least one urethane-forming catalyst selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfate salts, amine compounds and amine salts.

Examples of the tin catalyst include organotin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

Examples of the metal chloride include chlorides of metals selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. Examples of the metal chloride include divalent cobalt chloride, have.

The metal acetylacetonate salt is an acetylacetonate salt of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al and includes, for example, cobalt acetylacetonate, nickel acetylacetonate, Acetonate, and the like.

Examples of the metal sulfate include sulfate of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al, and examples thereof include copper sulfate.

Examples of the maleimide compound include polyfunctional aliphatic / alicyclic maleimide and polyfunctional aromatic maleimide. Examples of the polyfunctional aliphatic / alicyclic maleimide include N, N'-methylenebismaleimide, N, N'-ethylenebismaleimide, tris (hydroxyethyl) isocyanurate and aliphatic / alicyclic maleimide A maleimide ester compound of an isocyanurate skeleton obtained by dehydrating esterification of a carboxylic acid, a maleic anhydride skeleton of an isocyanurate skeleton obtained by urethanating tris (carbamate hexyl) isocyanurate and an aliphatic / alicyclic maleimide alcohol Isocyanurate skeleton poly-maleimides such as maleimide urethane compounds; (Maleimide ethyl carbonate), aliphatic / alicyclic maleimidic carboxylic acid and various aliphatic / cycloaliphatic polyols are dehydrated and esterified, or aliphatic / alicyclic polyhydric alcohols Aliphatic / alicyclic poly (maleimide) ester compounds obtained by transesterifying maleimide carboxylic acid esters with various aliphatic / cycloaliphatic polyols; Aliphatic / cycloaliphatic maleimide alcohols obtained by ether ring-opening reaction of aliphatic / alicyclic maleimidic carboxylic acid with various aliphatic / cycloaliphatic polyepoxides, aliphatic / cycloaliphatic maleimide alcohols and various aliphatic / alicyclic polyisocyanates Aliphatic / alicyclic poly (maleimide) urethane compounds obtained by urethanization reaction, and the like.

Examples of the polyfunctional aromatic maleimide include aromatic polyimide ester compounds obtained by dehydrating esterification of maleimide carboxylic acid and various aromatic polyols or transesterification of maleimide carboxylic acid esters with various aromatic polyols and maleimide carboxylic acid esters, Aromatic polyfunctional maleimide compounds such as aromatic polyimide compounds obtained by ether ring-opening reaction of various aromatic polyepoxides, aromatic polyimaleimide urethane compounds obtained by urethanization of maleimide alcohol with various aromatic polyisocyanates, and the like have.

Specific examples of the polyfunctional aromatic maleimide include N, N '- (4,4'-diphenylmethane) bismaleimide, N, N'-2,4-tolylene bismaleimide, N, N' Methylene-2,4-bismaleimide benzene, N, N'-m-phenylene bismaleimide, N, N'-p-phenylene bismaleimide, N, N'-m-toluylene bismaleimide, N, N'-4,4'-biphenylene bismaleimide, N, N'- N, N'-4,4 '- [3,3'-dimethyldiphenylmethane] bismaleimide, N, N'- Phenylmethane] bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N, N'-4,4'-diphenylpropanebismaleimide, N, N'- Diphenyl ether bismaleimide, N, N'-3,3'-diphenylsulfone bismaleimide, N, N'-4,4'-diphenylsulfone bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-t-butyl- Bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2 Methylphenyl) -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) Bis (1,1-dimethylethyl) benzene], 4,4'-methylene-bis [1- (4-maleimidophenoxy) Bis [1- (4-maleimidophenoxy) -2,6-di-s-butylbenzene], 4,4'-cyclohexylidene- 2-cyclohexylbenzene, 4,4'-methylenebis [1- (maleimidophenoxy) -2-nonylbenzene], 4,4 '- (1-methylethylidene) -bis [ - (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene, 4,4 '- (2-ethylhexylidene) ), 4,4'- (1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4'-cyclohexylidene-bis [1- (maleimidophenoxy) -3- Benzene], 2,2-bis [4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2- Bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2- Propane, 2,2-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] hexafluoropropane, 2,2- Phenyl] propane, 2,2-bis [3-ethyl- 4- (4-maleimidophenoxy) phenyl] hexafluoropropane, bis [ , Bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl] methane, bis [3-ethyl- (4-maleimidophenoxy) phenyl] methane, Phenyl] -tricyclo [5.2.1.0 ^2,6 ] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo [5.2.1.0 ^2,6 ] decane , 3,9-bis [4- (4- FIG) phenyl] - tricyclo [5.2.1.0 ^2,6] decane, 4,9- bis [4- (4-maleimidephenoxy) phenyl] - tricyclo [5.2.1.0 ^2,6] decane, Bis [3-methyl-4- (4-maleimidophenoxy) phenyl] mentane, 1,8-bis [4- 3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] mentane.

BMI-1000, BMI-1000, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H and BMI-4000 as commercial products of the maleimide compounds. , BMI-5100, BMI-7000, BMI-7000H and BMI-TMH (manufactured by Yamato Kasei Kogyo Co., Ltd.) and MIA-200 (manufactured by DIC Corporation).

These bismaleimide derivatives may be synthesized by a conventional method, or commercially available products may be used. Among the bismaleimide derivatives in particular, those which do not contain a halogen atom in the molecule are preferable from the viewpoint of not imposing a load on the environment. These may be used singly or in combination of two or more.

Examples of the benzoxazine compound include bisphenol A type benzoxazine, bisphenol F type benzoxazine, and bisphenol S type benzoxazine. As a commercially available product, "F-a" (manufactured by Shikoku Chemicals Corporation) can be mentioned.

The oxazoline compound is not particularly limited as long as it contains an oxazoline group. K-2010E, K-2020E, K-2030E, WS-500, WS-700 and RPS-1005 of Epochros (manufactured by Nippon Shokubai Co., Ltd.) are examples of these commercially available products.

Examples of the carbodiimide compound include dicyclohexylcarbodiimide and diisopropylcarbodiimide.

The cyclocarbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond. Examples include alkylene carbonate compounds having a polyfunctional structure.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ (3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [ (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, In addition to polyfunctional oxetanes such as oligomers and copolymers thereof, oxetane alcohol and novolak resins, poly (p-hydroxystyrene), cardo type bisphenols, calixarene, calix resorcinarene, And ether compounds with a hydroxyl group-containing resin such as sesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

As the episulfide resin, for example, YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation, and YSLV-120TE manufactured by Todo Gaseous Co., Ltd. and the like can be mentioned. An episulfide resin in which the oxygen atom of the epoxy group of the novolak type epoxy resin is substituted with a sulfur atom can also be used by using the same synthesis method.

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.

Examples of the epoxy resin include epoxy resins such as jER828, jER834, jER1001, jER1004, Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055 manufactured by DIC Corporation, Epotone YD-011 Epoxy ESA-011, ESA-014 and ELA-115 manufactured by Sumitomo Chemical Industries, Ltd., DER317, DER331, DER661 and DER664 manufactured by Dow Chemical Co., Ltd., YD-013, YD- ELA-128, AER330, AER331, AER661, and AER664 (all trade names) manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol A type epoxy resin; Epoxy resin YDB-400, YDB-500 manufactured by Tohto Kasei Co., DER542 manufactured by Dow Chemical Co., Sumi-epoxy resin manufactured by Sumitomo Chemical Co., Ltd., epoxy resin ESB-400, ESB-700, AER711 manufactured by Asahi Kasei Kogyo Co., Ltd. and AER714 (all trade names); JER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, Epotohto YDCN- Epoxies ESCN-195X, ESCN-701, and EPCN-201 of EI du Pont de Nemours & Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN- AERECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7 and YDCN-700-7 of Shinnitetsu Chemical Co., 10, YDCN-704 YDCN-704A, Epiclon N-680, N-690, and N-695 (all trade names) manufactured by DIC Corporation; Bisphenol F type epoxy resins such as Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Kagaku Kogyo Co., Ltd., Epitoto YDF-170, YDF-175 and YDF-2004 manufactured by Toto Kasei Co., Hydrogenated bisphenol A type epoxy resins such as Eptoto ST-2004, ST-2007, and ST-3000 (trade name) manufactured by Tokyo Kasei Kogyo; A glycidylamine type epoxy resin such as jER604 manufactured by Mitsubishi Chemical Corporation, an epoxy resin YH-434 manufactured by Tohto Kasei Co., and Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 (all trade names) manufactured by Daicel Chemical Industries, Ltd.; A trihydroxyphenylmethane type epoxy resin such as YL-933 available from Mitsubishi Chemical Corporation, T.E.N. available from Dow Chemical Co., EPPN-501, EPPN-502 (all trade names); Non-cisolene type or biphenol type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation or a mixture thereof; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., EPX-30 manufactured by Adeka Corporation and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak type epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resins such as jERYL-931 (all trade names) of Mitsubishi Chemical Corporation; A heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); A diglycidyl phthalate resin such as Nichiji-like blemish DGT; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd.; Epoxy resin containing naphthalene group such as ESN-190, ESN-360, HP-4032, EXA-4750 and EXA-4700 manufactured by Shin-Etsu Chemical Co., Ltd.; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as Nissi-like CP-50S and CP-50M; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; And CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Toyobo Co., Ltd.). However, the present invention is not limited thereto. Among them, bisphenol A type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, biphenol type epoxy resin or a mixture thereof is preferable.

These epoxy resins may be used alone or in combination of two or more.

(Thermosetting catalyst)

When the above-mentioned thermosetting component is contained, it is preferable to further contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-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. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Chemicals Corporation, DBU, U-CATSA102, U-CAT5002 (all bicyclic amidine compounds and salts thereof), and the like. In particular, it is not limited to these, and it may be any one that accelerates the reaction of a carboxyl group with at least one of a thermosetting catalyst of an epoxy resin or an oxetane compound, or an epoxy group and an oxetanyl group, It may also be used as a mixture of two or more species. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

The blending amount of the thermosetting catalyst is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass based on 100 parts by mass of the thermosetting component.

(coloring agent)

The photo-curable resin composition of the present invention may contain a colorant. As the coloring agent, publicly known coloring agents such as red, blue, green, and sulfur can be used, and any of pigments, dyes, and pigments may be used. Specifically, a color index (issued by C.I .; published by The Society of Dyers and Colors) is given. However, it is preferable that the coloring agent is a halogen-free coloring agent from the viewpoints of reduction in environmental load and influence on the human body.

Red colorant:

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.

Blue colorant:

Examples of the blue colorant include a phthalocyanine type and anthraquinone type, and the pigment type is classified into a pigment. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Green colorant:

Examples of the green colorant include phthalocyanine type, anthraquinone type and perylene type. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system.

In addition, a coloring agent such as purple, orange, brown or black may be added for the purpose of adjusting the color tone.

(Organic solvent)

The photo-curing resin composition may contain an organic solvent for the production of the resin composition, for preparing the filler in the slurry state, and for adjusting the viscosity for application to the substrate or the 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, diethylene glycol monoethyl ether acetate (carbitol 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 singly or as a mixture of two or more kinds.

(Other optional components)

In the photocurable resin composition of the present invention, components such as an elastomer, a mercapto compound, an adhesion promoter, a block copolymer, an antioxidant, and an ultraviolet absorber may be further blended, if necessary. These materials may be those known in the field of electronic materials. The photo-curing resin composition of the present invention may contain at least one of a thickener for known additives such as fine silica, hydrotalcite, organic bentonite and montmorillonite, a defoaming agent such as silicone, fluorine, and high molecular weight, and a leveling agent, Silane coupling agents such as thiazole-based and triazole-based silane coupling agents, rust inhibitors, and the like.

The photo-curable resin composition of the present invention can be prepared, for example, by the above-mentioned organic solvent with a viscosity suitable for the application method, and a dip coating method, a flow coating method, a roll coating method, a bar coater method, Curtain coating method and the like, and the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 DEG C, whereby a tack-free coating film can be formed.

As the above substrate, there may be used a substrate such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluorine / polyethylene / PPO (FR-4 and the like), other polyimide films, PET films, glass films, and the like using materials such as copper clad laminate for high-frequency circuit using poly (phenylene ether, polyphenylene oxide) A substrate, a ceramic substrate, a wafer plate, and the like.

The photocurable resin composition of the present invention may be applied on a film (hereinafter also referred to as a carrier film) and dried to form a dry film. In the case of dry film formation, the photo-curable resin composition of the present invention is diluted with the above organic solvent and adjusted to an appropriate viscosity, and the resulting mixture is applied to a developing roller such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, , A spray coater or the like to a uniform thickness on the carrier film and dried at a temperature of usually 50 to 130 ° C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 5 to 150 占 퐉, preferably 10 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is 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 5 to 150 mu m. And preferably in the range of 10 to 150 mu m.

It is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing the adherence of dust to the surface of the film after the film of the photocurable resin composition of the present invention is formed 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 May be smaller.

After the dry film of the present invention is brought into contact with the substrate by a laminator or the like so as to be in contact with the substrate, the resin insulating layer can be formed by peeling off the carrier film.

The volatile drying that is performed after coating the photocurable resin composition of the present invention on a substrate or on a carrier film can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like A method in which warm air in the dryer is countercurrently contacted with the air in the dryer, and a method in which air is sprayed onto the support from a nozzle).

By applying the photocurable resin composition of the present invention and volatilizing and drying the solvent, the resulting coating film or dry film is subjected to exposure (irradiation with active energy rays) to cure the exposed portion (the portion irradiated with the active energy rays) . Alternatively, a pattern exposure may be performed by a contact type (or a non-contact type) through a photomask having a pattern selectively exposed to an active energy ray by a direct exposure or laser direct exposure machine, and the unexposed portion may be exposed to a dilute alkali aqueous solution 0.3 to 3 wt% aqueous sodium carbonate solution) to form a resist pattern. If necessary, a pattern may be formed by laser processing.

As the exposure device used for the irradiation of the active energy ray, any device that mounts a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, or a mercury short arc lamp and irradiates ultraviolet rays in the range of 350 to 450 nm, A drawing apparatus (for example, a laser direct imaging apparatus for directly drawing an image with a laser by CAD data from a computer) can be used. As a laser light source of a direct shot, both a gas laser and a solid laser can be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. The exposure dose for image formation varies depending on the film thickness and the like, but may be generally within the range of 20 to 800 mJ / cm 2, preferably 20 to 600 mJ / cm 2.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developing solution, an alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

The method for producing a printed wiring board according to the present invention comprises a step of blending two or more kinds of fillers having different refractive indexes with one or more fillers as powders and one or more fillers in a slurry state. As described above, it is preferable that the particle size distribution D ₅₀ of the photo-curable resin composition is 3.0 μm or less and D ₉₀ is 8.0 μm or less. It is also preferable that at least one filler among the two or more fillers has a refractive index of less than 1.5 or more than 1.7 and is blended in a slurry state. Of the two or more fillers, one or more fillers preferably have a refractive index of 1.5 to 1.7 and are blended in powder form. Materials used in the method for producing a printed wiring board of the present invention are as described above.

<Examples>

The present invention will be described in more detail with reference to the following examples and comparative examples, but it goes without saying that the present invention is not limited to the following examples. In the following, &quot; part &quot; and &quot;% &quot; are on a mass basis unless otherwise specified.

(Synthesis Example 1: Synthesis of carboxyl group-containing resin (A-1)

119.4 g of novolak type cresol resin (Shonad CRG951, OH equivalent: 119.4), 1.19 g of potassium hydroxide, and 119.4 g of toluene were added to an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device and a stirring device. g, 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 gradually added dropwise, and the mixture was reacted at 125 to 132 캜 at 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 the potassium hydroxide to obtain a propylene oxide of a novolac cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / To obtain a reaction solution. It was found that an average of 1.08 moles of alkylene oxide per 1 equivalent of the phenolic hydroxyl group was obtained. 293.0 g of the alkylene oxide reaction solution of the obtained novolak type 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, The mixture was blown at a rate of 10 ml / min and reacted at 110 캜 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 solution of sodium hydroxide, and then washed with water. Thereafter, toluene was distilled off by replacing the toluene with 118.1 g of diethylene glycol monoethyl ether acetate (carbitol acetate) by an evaporator 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 slowly added, and the reaction was carried out at 95 to 101 ° C for 6 hours. To obtain a carboxyl group-containing resin having an acid value of 88 mg KOH / g and a solid content of 71%. This is designated as Resin Solution A-1.

(Synthesis Example 2: Synthesis of carboxyl group-containing resin (A-2)

To 600 g of diethylene glycol monoethyl ether acetate (carbitol acetate), 1070 g of an orthocresol novolak type epoxy resin (Epiclon N-695 manufactured by DIC, softening point 95 캜, epoxy equivalent 214, average functional group number 7.6), 360 g of acrylic acid, And the mixture was heated 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 aromatic hydrocarbon (Solvesso 150) and 456.0 g of tetrahydrophthalic anhydride were added to the obtained reaction solution, and the reaction was carried out at 110 DEG C for 4 hours. After cooling, the mixture was allowed to contain a carboxyl group content of 89 mgKOH / g and a solid content of 65% To obtain a resin. This is designated as resin solution A-2.

(Evaluation of Refractive Index)

The refractive indices of the resins (solid components) of the resin solutions A-1 and A-2 obtained above were measured at 589.3 nm and 25 占 폚 using a refractive index meter ER-7MW manufactured by ERMA. The results are shown in Table 1 together with the refractive indices of silica, alumina, barium sulfate, and hydrotalcite.

(Preparation of silica slurry)

(Carbital acetate) as a solvent and 5 g of a vinyl silane coupling agent as a silane coupling agent were mixed and stirred, and the mixture was stirred with a bead mill to prepare a mixture solution of 0.5 g / m &lt; 2 &gt; Of dispersed zirconia beads. This was repeated 3 times to prepare a silica slurry filtered with a 3 탆 filter.

(Production of alumina slurry)

700 g of alumina (ASFP-20 manufactured by DENKA CO., LTD.), 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent and 5 g of a wet dispersant were mixed and stirred and dispersed by a bead mill. This was repeated three times to prepare an alumina slurry filtered with a 3 mu m filter.

(Preparation of barium sulfate slurry)

700 g of barium sulfate (B-30, manufactured by SAKAI KAGAKU KOGYO CO., LTD.), 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5 g of a wet dispersant were mixed and stirred and dispersed with a bead mill . This was repeated three times to prepare a barium sulfate slurry filtered with a 3 탆 filter.

(Preparation of hydrotalcite slurry)

700 g of hydrotalcite (DHT-4A, manufactured by Kyowa Chemical Industry Co., Ltd.), 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5 g of a wet dispersant were mixed and stirred. I did. This was repeated 3 times to prepare a hydrotalcite slurry which was filtered with a 3 탆 filter.

&Lt; Examples 1 to 5 and Comparative Examples 1 to 4 >

The above resin solution and slurry were mixed in the formulations (parts by mass) shown in Table 2, premixed by a stirrer, and then kneaded by a three-roll mill to obtain the sights of Examples 1 to 5 and Comparative Examples 1 to 4 To prepare a chemical conversion resin composition.

Here, the degree of dispersion of the obtained photo-curing resin composition was evaluated by particle size measurement by a grindmeter manufactured by Ericens Co., and it was 15 탆 or less.

The meanings of subscript numbers in Table 2 are as follows.

* 1: SO-E2 manufactured by Admatech Co.

* 2: ASFP-20 manufactured by Denka Co.

* 3: B-30 manufactured by Sakai Chemical Industry Co., Ltd.

* 4: DHT-4A manufactured by Kyowa Chemical Industry Co., Ltd.

* 5: Dipentaerythritol hexaacrylate

* 6: phenol novolak type epoxy resin

* 7: Triglycidyl isocyanurate

* 8: Melamine

* 9: 2,4,6-Trimethylbenzoyldiphenylphosphine oxide

* 10: Pigment Blue 15: 3

* 11: Pigment Yellow 147

* 12: Silicone antifoaming agent

* 13: Dipropylene glycol monomethyl ether

(Particle size distribution)

The photo-curing resin compositions of Example 3 and Comparative Example 2 were measured for particle size distribution by a microtrack (MT3300EX manufactured by Nikkiso Co., Ltd.). The results of Example 3 and Comparative Example 2 are shown in Fig. 1 and Fig. 2, respectively. D ₅₀ of Example 3 was 0.41 탆, and D ₉₀ was 1.7 탆. The D ₅₀ of Comparative Example 2 was 3.7 탆 and the D ₉₀ was 8.1 탆.

Characteristic evaluation:

The photocurable resin compositions of the above Examples and Comparative Examples were coated on the entire surface by screen printing on a patterned copper foil substrate and dried in a hot air circulation type drying furnace at 80 캜 for 30 minutes and cooled to room temperature to obtain an evaluation substrate . The properties of the obtained evaluation substrate were evaluated as follows.

In the following evaluation, the pattern formation of the photocurable resin composition was carried out by exposing the obtained evaluation substrate to an optimal exposure dose using a high-pressure mercury lamp mounted exposure apparatus (mercury short arc lamp mounted exposure apparatus, manufactured by Oak Seascus Co., Ltd.) At a temperature of 30 占 폚, a spraying pressure of 0.2 MPa, and a developing solution: 1 mass% sodium carbonate aqueous solution for 60 seconds. The optimum exposure dose was exposed through a step tablet (T4105C, manufactured by Stouffer Co.) at the time of exposure, and when the number of stages of remaining step tablets after development was 8, the optimum exposure dose was used. After the formation of the pattern, ultraviolet rays were irradiated under the conditions of an integrated exposure dose of 1000 mJ / cm 2 by a UV conveyer and then heated at 160 캜 for 60 minutes to cure the patterned photocurable resin composition.

(Resolution)

On the obtained evaluation substrate, an opening pattern of the photocurable resin composition was formed under the above conditions using a negative pattern having a via opening diameter of 60 占 퐉 as a negative mask for resolution evaluation and cured. The diameter of the opening in the bottom portion was observed and measured by a scanning electron microscope having a magnification of 1000 times and evaluated under the following evaluation conditions.

?: Diameter exceeding 55 占 퐉 and below 60 占 퐉

?: Diameter exceeding 50 占 퐉 and not exceeding 55 占 퐉

X: Diameter of 50 占 퐉 or less

(Crack resistance)

A pattern of the photocurable resin composition was formed on the obtained evaluation substrate under the above-described conditions using a negative pattern having a square hole as a negative mask for resolution evaluation and cured. Thereafter, a heat history was applied with one cycle at -55 占 폚 for 30 minutes and at 125 占 폚 for 30 minutes. After 1000 cycles, observations were made under an optical microscope and evaluated under the following evaluation conditions.

◎: No crack occurred

○: Crack occurred

X: Crack occurrence remarkable

(HAST resistance)

An evaluation substrate was obtained under the same conditions as above, except that a photocurable resin composition was applied to a BT substrate on which a comb electrode (line / space = 50 micrometers / 50 micrometers) was formed instead of the patterned copper foil substrate. The obtained photocurable resin composition on the evaluation substrate was cured under the same conditions as above to form a cured coating film. The substrate thus obtained was placed in a high-temperature high-humidity bath under an atmosphere of 130 ° C and a humidity of 85%, charged with a voltage of 12 V, and subjected to a HAST test in a bath for 168 hours. The insulation resistance value in the tank at the elapsing time of 168 hours was evaluated according to the following criteria.

◎: More than 10 ⁸ Ω

○: 10 ⁶ Ω less than 10 ⁸ Ω

×: 10 ⁶ Ω or less

(Haze value)

Each of Examples 1 to 5 and Comparative Examples 1 to 4, in which only the carboxyl group-containing resin and the filler component in Table 2 were mixed and dispersed, was applied onto a glass substrate with an applicator and dried in a hot air circulating type drying furnace at 80 캜 for 30 minutes To obtain a dry coating film having a thickness of 25 mu m. The haze value of this dry coating film was measured by an ultraviolet visible spectrophotometer (V-600 manufactured by Nippon Bunko Co., Ltd.). Haze value = diffuse transmittance / total light transmittance x 100 (%), and the larger the value is, the more the light is diffused. When the haze value is small, the light is difficult to diffuse, and thus the resolution is excellent.

* 1: In Comparative Example 3, since the amount of the solvent was excessively large, the coating film formability was insufficient and evaluation was impossible.

As is clear from the results shown in Table 3 above, the photocurable resin composition of the present invention can obtain a cured product having good resolution even though it contains a plurality of kinds of fillers having different refractive indexes. On the other hand, the photo-curing resin compositions shown in the comparative examples had poor performance as a photo-curable resin composition, such as poor resolution and poor film formability.

Claims (10)

1. A photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, and two or more fillers having different refractive indexes,
Wherein at least one filler among the two or more fillers is blended as a powder and at least one filler is blended in a slurry state. The photo-curable resin composition according to claim 1, wherein the photo-curable resin composition has a particle size distribution D ₅₀ of 3.0 탆 or less and a D ₉₀ of 8.0 탆 or less. The photocurable resin composition according to claim 1, wherein one or more fillers among the two or more fillers have a refractive index of less than 1.5 or more than 1.7 and are blended in a slurry state. The photocurable resin composition according to claim 1, wherein one or more fillers among the two or more fillers have a refractive index of 1.5 to 1.7 and are blended in powder form. The photocurable resin composition according to claim 1, wherein the carboxyl group-containing resin has an aromatic ring. The photocurable resin composition according to claim 1, wherein the carboxyl group-containing resin comprises a carboxyl group-containing resin obtained by using a phenol compound as a starting material. The photocurable resin composition according to claim 1, further comprising a photoreactive monomer. A dry film obtained by applying the photo-curable resin composition according to claim 1 onto a film and drying the film. A cured product obtained by applying the photo-curable resin composition according to claim 1 or the photo-curable resin composition according to claim 1 onto a film and drying the obtained dry film by at least one of irradiation with active energy ray and heating, And the printed circuit board. A method for producing a photocurable resin composition, which comprises a step of mixing two or more kinds of fillers having different refractive indexes, one or more fillers as a powder, and one or more fillers in a slurry state.

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