TW201425434A - Photocurable resin composition, printed wiring board, and method for producing photocurable resin composition - Google Patents

Abstract

Provided is a photocurable resin composition which is capable of providing a cured product having good resolution even though a plurality of kinds of fillers having different refractive indexes are contained therein. A photocurable resin composition which contains a carboxyl group-containing resin, a photopolymerization initiator and two or more kinds of fillers having different refractive indexes. This photocurable resin composition is characterized in that, among the two or more kinds of fillers, one or more kinds of fillers are blended in the form of powders and one or more kinds of fillers are blended in the form of slurries.

Description

Photocurable resin composition, printed wiring board, and photocurable resin composition manufacturing method

The present invention relates to a photocurable resin composition, a printed wiring board, and a method for producing a photocurable resin composition. More specifically, it is possible to obtain a solution even if a plurality of fillers having different refractive indices are contained. A photocurable resin composition of a cured product having good properties, a printed wiring board having the cured product, and a method for producing the photocurable resin composition.

In general, in a printed wiring board used for an electronic device or the like, in order to prevent the solder from adhering to an unnecessary portion and preventing the conductor of the circuit from being exposed, it is corroded by oxidation or moisture, and is connected to the substrate on which the circuit pattern is formed. The area of the hole forms a solder resist.

As one of the methods of forming a solder resist of a desired pattern on a substrate, a method of forming using photolithography is used. For example, a photosensitive anti-solder resist composed of an alkali-developable photocurable resin composition is exposed to a pattern mask, and then alkali-developed to form a base by the exposed portion and the non-exposed portion. The difference in solubility of the developer forms a pattern.

As one of the improved means of the properties of the solder resist, such as curing shrinkage suppression, heat resistance, adhesion, or hardness, conventionally, an inorganic filler or an organic filler is blended in the solder resist (for example, Patent Documents 1 and 2) ). Each of the various types of fillers has its own advantages and disadvantages. In recent years, the use of solder resists has been improved with the increase in the density of printed wiring boards, which is associated with the increase in density of electronic devices. The filler is blended with a plurality of fillers to enhance the effect of the filler.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-053448

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-236363

However, when a plurality of kinds of fillers are blended in the photosensitive solder resist, when the refractive indices between the fillers are different, good resolution cannot be obtained, and a fine pattern may not be formed.

Therefore, it is an object of the present invention to provide a photocurable resin composition having a cured product having excellent resolution, a dry film, and a cured product obtained by curing a plurality of kinds of fillers having different refractive indexes. A printed wiring board having the cured product and a method of producing the photocurable resin composition.

In order to solve the above problems, the inventors of the present invention have found that the above problems can be solved by using a plurality of kinds of fillers having different refractive indices in a powder state and a slurry state, and the present invention has been completed.

In other words, the photocurable resin composition of the present invention comprises a resin containing a carboxyl group, a photopolymerization initiator, and a photocurable resin composition having two or more kinds of fillers having different refractive indices, and is characterized in that Among the above two or more types of fillers, one or more types of fillers are blended in a powder form, and one or more types of fillers are blended in a slurry state.

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

In the photocurable resin composition of the present invention, one or more of the above-described two or more types of fillers preferably have a refractive index of less than 1.5 or more than 1.7 and are blended in a slurry state.

In the photocurable resin composition of the present invention, one or more of the above-described two or more types of fillers preferably have a refractive index of 1.5 to 1.7 and are blended with a powder.

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

The photocurable 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 contains a photoreactive monomer.

The dry film of the present invention is characterized by any of the foregoing The photocurable resin composition is obtained by coating and drying the film.

The printed wiring board of the present invention is characterized in that it has a cured product which is hardened by at least either of the photocurable resin composition of the above or the dry film by irradiation with an active energy ray and heating. And get it.

The method for producing a photocurable resin composition according to the present invention is characterized in that it contains two or more kinds of fillers having different refractive indices, and one or more kinds of fillers are used as a powder, and one or more kinds of fillers are in a slurry state. The step of blending.

According to the present invention, it is possible to provide a photocurable resin composition, a dry film, and a cured product obtained by curing a plurality of types of fillers having different refractive indices and having excellent resolution. A printed wiring board comprising the cured product and a method of producing the photocurable resin composition.

Fig. 1 is a graph showing the results of measuring the particle size distribution of the photocurable resin composition of Example 3 by a laser diffraction scattering particle diameter particle size distribution measuring apparatus.

2] FIG. 2 is a view showing a photocurable resin composition for measuring a filler of only a powder blended by a laser diffraction scattering particle diameter particle size distribution measuring apparatus. (Graph of Comparative Example 2).

The photocurable resin composition of the present invention contains a carboxyl group-containing resin, a photopolymerization initiator, and a photocurable resin composition having two or more kinds of fillers having different refractive indices, and is of two or more kinds thereof. Among the fillers, one or more types of fillers are blended in a powder, and one or more types of fillers are blended in a slurry state. Even if two or more kinds of fillers having different refractive indices are blended, the filler is blended in a slurry state, whereby the transparency of the photocurable resin composition is improved, and a cured product having good resolution can be obtained. In addition, by blending one or more kinds of fillers in a powder state without blending all of the fillers, it is possible to suppress an increase in the amount of the solvent, deterioration in drying properties, and the like, and to secure good workability.

The filler can form an aggregate in the photocurable resin composition, but the photocurable resin composition of the present invention has a smaller particle size in the composition than in the case where the filler is only blended with the powder. . The photocurable resin composition of the present invention has a particle size distribution D ₅₀ of 3.0 μm or less and D ₉₀ of 8.0 μm or less, _more preferably D ₅₀ of 1.0 μm or less and D ₉₀ of 3.0 μm or less. In the present specification, the particle diameter when the cumulative % of the small particle diameter as a result of the particle size distribution measurement is 50% is referred to as the particle size distribution D ₅₀ , and the particle diameter at the time of 90% is referred to as the particle size distribution D ₉₀ . The particle size distributions D ₅₀ and D ₉₀ can be measured, for example, by a laser diffraction scattering method using MT3300EX manufactured by Nikkiso Co., Ltd.

The refractive index of the filler blended in the slurry state is preferably less than 1.5 or more than 1.7. It is because the filler of such refractive index is in the form of a slurry. When the state is blended, better resolution can be obtained. In such a refractive index, it is considered that the difference in refractive index of the resin of the photocurable resin composition is large, and the wettability at the interface between the filler blended with the powder and the resin is insufficient, and light refraction is easily caused, and light is easily generated. Scattering. When the filler having such a refractive index is blended in a slurry state, it is considered that the wettability of the filler and the resin is improved, and scattering of light can be suppressed, so that 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 even if it is blended with the powder to obtain good resolution. Moreover, it is considered that the coating film to which the photocurable resin composition of the present invention is applied has a low reflectance, and therefore the filler is uniformly dispersed.

[Resin containing carboxyl group]

The resin containing a carboxyl group can be used for various conventionally known carboxyl group-containing resins having a carboxyl group in a molecule. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond in a molecule is preferred in terms of photocurability and development resistance. The ethylenically unsaturated double bond is preferably derived from acrylic acid or methacrylic acid or such derivatives. When only a carboxyl group-containing resin having no ethylenic unsaturated double bond is used, in order to make the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule, that is, photoreactivity, which is described later. monomer.

Specific examples of the resin containing a carboxyl group include the following compounds (either an oligomer and a polymer).

(1) The inclusion of an unsaturated carboxylic acid such as (meth)acrylic acid with styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene or the like A resin containing a carboxyl group obtained by copolymerization of a compound having an unsaturated group.

(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid A diol compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide addition diol, and a phenol A carboxyl group-containing urethane resin obtained by addition polymerization of a diol compound such as a hydroxyl group or an alcoholic hydroxyl group.

(3) by diisocyanate, with bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dimethicone type epoxy resin Photosensitive polymerization of a (meth) acrylate or a partial acid anhydride modified product thereof, a diol compound containing a carboxyl group, and a diol compound by a bifunctional epoxy resin such as a biphenol-based epoxy resin Amino urethane resin.

(4) In the resin synthesis of the above (2) or (3), a compound having one hydroxyl group and one or more (meth)acrylonium groups in a molecule such as a hydroxyalkyl (meth)acrylate is added, and the terminal is added. A (meth)acrylic acid-containing photosensitive urethane resin containing a carboxyl group.

(5) In the resin synthesis of the above (2) or (3), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to the molecule, and one isocyanate group and one or more are added in the molecule (A) A photosensitive urethane resin containing a carboxyl group as a compound of an acrylonitrile group and a terminal (meth) propylene.

(6) A photosensitive resin containing a carboxyl group in which a (meth)acrylic acid is reacted with a polyfunctional (solid) epoxy resin having a bifunctional or higher functional group to be described later, and a hydroxyl group of a side chain is added to form a dibasic acid anhydride.

(7) reacting (meth)acrylic acid with a polyfunctional epoxy resin which further epoxidizes a hydroxyl group of a bifunctional (solid) epoxy resin as described later with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl group. A photosensitive resin containing a carboxyl group.

(8) reacting a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid with a bifunctional oxetane resin as described later, and adding a hydroxy group to the produced hydroxy group A carboxyl group-containing polyester resin of a dibasic acid anhydride such as formic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

(9) reacting a monocarboxylic acid containing an unsaturated group with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide. The reaction product is further reacted with a polybasic acid anhydride to obtain a photosensitive resin containing a carboxyl group.

(10) reacting a reaction product obtained by reacting a monocarboxylic acid having an unsaturated group with a cyclic carbonate compound obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethyl orthocarbonate The obtained reaction product is further reacted with a polybasic acid anhydride to obtain a photosensitive resin containing a carboxyl group.

(11) Photosensitive property of a carboxyl group obtained by further adding a resin having one epoxy group and one or more (meth) acryloyl group in one molecule to the resin of the above (1) to (10) Resin.

Furthermore, in the present specification, (meth) acrylate is a generic name for acrylate. The terms of methacrylate and mixtures of these are the same.

The above-mentioned resin containing a carboxyl group, in the main skeleton. The side chain of the polymer has a plurality of carboxyl groups and thus can be developed with a dilute aqueous alkali solution.

Further, 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. When the acid value of the carboxyl group-containing resin is 40 mgKOH/g or more, the alkali development is good. On the other hand, when it is 200 mgKOH/g or less, the dissolution of the exposed portion due to the developer can be suppressed, so that it is possible to suppress the line width and the like. Thin or, depending on the situation, the exposed portion and the unexposed portion are dissolved and peeled off in a developing solution without distinction, and the resist pattern can be satisfactorily drawn.

Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is generally preferably from 2,000 to 150,000, more preferably from 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tackfree performance is good, and the moisture resistance of the coating film after the exposure is good, and the film can be prevented from being reduced during development, and the resolution can be suppressed from being lowered. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

The blending amount of the carboxyl group-containing resin is suitably in the range of 20 to 60% by mass, preferably 30 to 50% by mass, based on the photocurable resin composition. When the blending amount of the carboxyl group-containing resin is 20% by mass or more, the film strength is good, which is preferable. On the other hand, when it is 60% by mass or less, the tackiness of the photocurable resin composition does not become too high, and the coatability to the carrier film or the like is good, which is preferable.

The resin containing a carboxyl group is not limited to the above-mentioned ones, and may be used singly or in combination of plural kinds. In particular, among the above-mentioned carboxyl group-containing resins, the resin having an aromatic ring has a high refractive index and excellent resolution, and therefore, it is preferable to further have a novolac structure, and it is excellent in resolution and PCT and crack resistance. Preferably. In particular, the carboxyl group-containing resin synthesized using a phenol compound as a starting material is excellent in HAST resistance and PCT resistance as in the case of the above-mentioned carboxyl group-containing resin (9) and (10), and is also excellent in low CTE in the present invention. As a result, the crack resistance is also excellent, and therefore it can be suitably used. Moreover, such a resin containing a carboxyl group can also be obtained as a resin which does not have a hydroxyl group. In general, the presence of a hydroxyl group also has excellent characteristics such as an improvement in adhesion due to hydrogen bonding, but it is known that moisture resistance is remarkably lowered. Specifically, the phenol resin in which the phenol novolac resin is oxidized and alkylated is partially propylene-deuterated, and an acid anhydride is introduced, whereby the double bond equivalent weight of 300 to 550 and the acid value of 40 to 120 mg KOH/g can be easily obtained. A resin that does not theoretically have a hydroxyl group.

[Photopolymerization initiator]

The photopolymerization initiator is not particularly limited, and a photopolymerization initiator selected from the group consisting of an oxime ester-based photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a fluorenylphosphine oxide-based photopolymerization can be suitably used. One or more photopolymerization initiators of the group consisting of a starter and a titanocene photopolymerization initiator.

It is preferable that the amount of the oxime ester-based initiator added is small, that is, it is sufficient, and the gas is suppressed, so that PCT resistance or crack resistance is effective. The above-mentioned fluorenylphosphine oxide photopolymerization initiator is longer than 400 nm Since the wavelength has absorption, it is preferable that the deep hardenability is high. Further, in addition to the oxime ester-based initiator, when a fluorenylphosphine oxide-based photopolymerization initiator is used in combination, a shape having good resolution is obtained, which is particularly preferable. The above-mentioned titanocene-based photopolymerization initiator has a wide light absorption wavelength region, is excellent in deep hardenability, and has high photoreactivity. Therefore, it is sufficient that the amount of exposure necessary for curing is small, and high production can be achieved.

The oxime ester photopolymerization initiator is commercially available, and CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF JAPAN Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., NCI-831, and the like are mentioned. Further, a photopolymerization initiator having two oxime ester groups in the molecule may be suitably used, and specifically, an oxime ester compound having a carbazole structure represented by the following general formula may 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 (alkyl group having 1 to 17 carbon atoms, and carbon number 1 to 8) Alkoxy group, amine group, alkylamino group or dialkylamino group having an alkyl group having 1 to 8 carbon atoms, naphthyl group (alkyl group having 1 to 17 carbon atoms, and alkyl group having 1 to 8 carbon atoms) An oxy group, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 ~8 alkoxy, halo, phenyl, phenyl (alkyl via 1 to 17 carbon atoms) , an alkoxy group having 1 to 8 carbon atoms, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, or a naphthyl group (alkyl group having 1 to 17 carbon atoms) Alkoxy group having 1 to 8 carbon atoms, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, a fluorenyl group, a pyridyl group, a benzofuranyl group, a benzothiophene group a group, Ar represents a bond, or an alkyl group having a carbon number of 1 to 10, a vinyl group, a phenyl group, a phenyl group, a phenyl group, a thiophene group, a thiophene group, a thiophene group, a thiophene group, and a thiophene group. Furanyl, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2'-styrene-diyl, n is an integer of 0 or 1.)

In particular, in the above general formula, it is preferred that X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, or a phenyl group, a naphthyl group, a thiophene group or Thionyl group.

Moreover, as a preferable carbazole oxime ester compound, the compound which can be represented by the following general formula is mentioned.

(wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted by 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 which may be substituted by an alkyl group having 1 to 4 carbon atoms or an alkoxy group.

R ³ may be bonded via an oxygen atom or a sulfur atom, and represents an alkyl group having 1 to 20 carbon atoms which may be substituted by a phenyl group, and a benzyl group which may be substituted with an alkoxy group having 1 to 4 carbon atoms.

R ⁴ represents a nitro group or a fluorenyl group represented by XC(=O)-. X represents an aryl group, a thienyl group, a morpholinyl group, a phenylthio group or a structure represented by the following formula which may be substituted with an alkyl group having 1 to 4 carbon atoms.

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

The blending amount of the oxime ester photopolymerization initiator is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 parts by mass or more, the photocurability on copper is good, the peeling of the coating film is suppressed, and the coating properties such as chemical resistance are also good. On the other hand, when it is 5 parts by mass or less, the light absorption on the surface of the solder resist coating film is good, and the deep hardenability is improved. More preferably 0.5 to 3 parts by mass.

The α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1,2-benzyl 2--2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and the like. Commercially available products include Irgacure 907, Irgacure 369, Irgacure 379, and the like manufactured by BASF JAPAN.

The mercapto phosphine oxide-based photopolymerization initiator may specifically be 2,4,6-trimethylbenzylidenediphenylphosphine oxide or bis(2,4,6-trimethylbenzylidene). - phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO, Irgacure 819, and the like manufactured by BASF JAPAN.

The amount of the α-aminoacetophenone-based photopolymerization initiator and the fluorenylphosphine oxide-based photopolymerization initiator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. . When the amount is 0.01 parts by mass or more, the photocurability on copper is good, the peeling of the coating film is suppressed, and the coating properties such as chemical resistance are good. On the other hand, when it is 15 parts by mass or less, the outgas is reduced, and the light absorption on the surface of the coating film is good, and the deep hardenability is improved. More preferably, it is 0.5 to 10 parts by mass.

The titanocene-based photopolymerization initiator may specifically be bis(cyclopentadienyl)-di-phenyl-titanium, bis(cyclopentadienyl)-di-chloro-titanium, bis(cyclopentane) Dienyl)-bis(2,3,4,5,6-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 Co., Ltd., and the like.

The blending amount of the titanocene-based photopolymerization initiator is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the amount is 0.01 parts by mass or more, the photocurability on copper is good, the peeling of the coating film is suppressed, and the coating properties such as chemical resistance are good. On the other hand, when it is 15 parts by mass or less, the amount of light absorption does not become excessively high, and the deep hardenability is good. More preferably, it is 0.05 to 10 parts by mass.

Photopolymerization of the photocurable resin composition of the present invention In addition to the starter, a photoinitiator or a sensitizer can be used. A photoinitiator and a sensitizer which are suitable for use, and examples thereof include a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, a benzophenone compound, and a tertiary amine compound. And xanthone compounds and the like.

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

The acetophenone compound specifically includes, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, and 1 , 1-dichloroacetophenone and the like.

Specific examples of the ruthenium compound include 2-methyloxime, 2-ethylhydrazine, 2-t-butylhydrazine, 1-chloroindole and the like.

The thioxanthone compound, specifically, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthene Ketones, etc.

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

Specific examples of the benzophenone compound include benzophenone, 4-benzylguanidino diphenyl sulfide, 4-benzylindolyl-4'-methyldiphenyl sulfide, and 4-benzyl fluorenyl group. -4'-ethyldiphenyl sulfide, 4-benzylindolyl-4'-propyldiphenyl sulfide, and the like.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound and a compound having a dialkylaminobenzene structure. For example, commercially available products include 4,4'-dimethylaminobenzophenone (Japan Soda). Nissocure MABP), 4,4'-diethylaminobenzophenone Dialkylaminobenzophenone, such as EAB), 7-(diethylamino)-4-methyl-2H-1-benzopipene-2-one (7-(diethyl) a coumarin compound containing a dialkylamine group such as an amino)-4-methylcoumarin), ethyl 4-dimethylamino benzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-two Methylamino benzoic acid ethyl ester (Quantacure DMB manufactured by International Bio-synthetics Co., Ltd.), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by International Bio-synthetics Co., Ltd.), p-dimethyl Isoamyl ethyl amide benzoate (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-ethylhexyl 4-dimethylaminobenzoate (Esolol 507 manufactured by Van Dyk Co., Ltd.), and the like.

Among these, a thioxanthone compound and a tertiary amine compound are preferable. In particular, a thioxanthone compound is preferred in terms of deep hardenability. Particularly preferred is thioxanthone containing 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, and the like. Compound.

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

Further, as the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and among them, a dialkylaminobenzophenone compound and a dialkyl group having a maximum absorption wavelength in the range of 350 to 450 nm are preferable. Amino-based coumarin compounds and ketocoumarins are particularly preferred.

As the dialkylaminobenzophenone compound, the toxicity of 4,4'-diethylaminobenzophenone is also low, which is preferable. Since the coumarin compound containing a dialkylamine group has a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, the coloring is small, and of course, a colorless and transparent photocurable resin composition can be provided, and a coloring pigment can be provided to reflect A colored anti-solder film of the color of the coloring pigment itself. In particular, 7-(diethylamino)-4-methyl-2H-1-benzopipene-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The blending amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the tertiary amine compound is 0.1 part by mass or more, a good sensitizing effect can be obtained. On the other hand, when it is 20 parts by mass or less, the light absorption of the surface of the dry solder resist film by the tertiary amine compound does not become too intense, and the deep hardenability becomes good. More preferably, it is 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiating aids, and sensitizers may be used singly or as a mixture of two or more kinds.

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

[filler]

In the photocurable resin composition of the present invention, two or more types of fillers having different refractive indices are blended, and the inventors have found that two or more kinds of fillers are used. In the material, one or more kinds of fillers are blended in a powder, and one or more kinds of fillers are blended in a slurry state, and the transparency of the photocurable resin composition is improved, and the resolution is improved. Further, by filling 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, less than 1.5, or more than 1.7 is blended in a slurry state as compared with powder blending. In the case of higher resolution. When the amount of the filler to be mixed in the slurry state is increased, the amount of the solvent is increased, the drying property is deteriorated, and the workability is also lowered. By blending all the fillers in a slurry state, the powder is blended, and the resolution is solved. Good at the same time, it can also improve drying or workability. In terms of obtaining better resolution, the refractive index of the powder-blended filler is preferably from 1.5 to 1.7, more preferably from 1.5 to 1.65. Further, since the coating film of the photocurable resin composition of the present invention is applied and the transmittance is low, it is considered that the filler is uniformly dispersed.

In the present invention, the powder is not particularly limited as long as the filler is in a powder form, and a known one can be used. In the present invention, the primary particle diameter means the average primary particle diameter (D ₅₀ ), which can be measured by a laser diffraction scattering method. Further, the total amount of the filler blended with the powder is preferably 75% or less, more preferably 0.1 to 60%, based on the total mass of the total filler. When the blending amount of the filler is 75% or less of the total amount of the composition, the viscosity of the insulating composition does not become excessively high, and the coating and moldability are good, and the cured product is less likely to become brittle.

The slurry state refers to a state in which a filler is dispersed in a liquid such as water or an organic solvent. A filler having a small primary particle size tends to agglomerate when mixed with a liquid, and therefore is filtered through a filtration membrane, and a large aggregate is preferably used after being removed. In order to remove a large aggregate, it is preferred to filter through a filtration membrane of 10 μm or less, and more preferably through a filtration membrane of 5 μm or less. The amount of the filler in the slurry is preferably from 10 to 90%, more preferably from 10 to 80%. When it is 10% or more, the workability deterioration due to a decrease in viscosity or the like can be suppressed, and when it is 90% or less, the dispersion stability as a slurry does not become too low, and the suppression of aggregation becomes good. The primary particle diameter of the filler blended with the powder and the filler blended in the slurry state is preferably different, and at this time, the filler can be blended with high filling. When the filler having a small primary particle size is easily aggregated in the case of a powder, it is preferable to mix a filler having a primary particle diameter of 1 μm or less in a slurry state, so that the filler can be blended with higher filling. Further, the total amount of the solid components of the filler blended in the slurry state is preferably 10 to 90%, more preferably 20 to 90%, and even more preferably 40% of the total solid content of all the fillers in terms of mass. ~90%. When it is 10% or more, the effect of improving transparency is good, and when it is 90% or less, the amount of the solvent in the composition does not become too large, and deterioration of drying property or sedimentation of the filler component after storage can be suppressed.

The liquid to be mixed with the filler in order to be in a slurry state is not particularly limited, and examples thereof include water or an aqueous solution, and an organic solvent to be described later.

The method of blending the filler in the powder and the slurry state is not particularly limited, and may be in the form of a powder or a slurry when mixed with other components such as a carboxyl group-containing resin at the time of blending before preliminary mixing.

In the present invention, a conventionally known inorganic filler or organic filler can be used as the filler. Examples of the inorganic filler include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural cerium oxide, synthetic cerium oxide, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, Aluminum hydroxide, aluminum oxide, magnesium hydroxide, talc, mica, hydrotalcite, aluminum citrate, magnesium citrate, calcium citrate, burnt talc, ash, potassium titanate , magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, hard calcite, boron nitride, aluminum borate, cerium oxide ball, glass cullet, glass sphere, cerium oxide, iron slag, copper, iron, Iron oxide, carbon black, Sandast alloy, AlNiCo magnet, magnetic powder of various ferrite grains, cement, glass powder, diatomaceous earth, antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, alum Wait. It is particularly preferable to use ceria, barium sulfate, talc, hydrotalcite or the like.

Examples of the inorganic filler having a refractive index of less than 1.5 include cerium oxide (refractive index: 1.45), potassium (refractive index: 0.07), and potassium hydrogencarbonate (refractive index: 1.48). Examples of the inorganic filler having a refractive index of more than 1.7 include zinc sulfide (refractive index: 2.37), zirconia (refractive index: 2.4), alumina (refractive index: 1.76), chromium oxide (refractive index: 2.5), and cadmium oxide (refraction). Rate: 2.49), cadmium sulfide (refractive index: 2.5), zinc oxide (refractive index: 1.95), titanium oxide (refractive index: 2.52-2.71), iron (refractive index: 2.36), copper oxide (refractive index: 2.71) Copper sulfide (refractive index: 1.73). Examples of the inorganic filler having a refractive index of 1.5 to 1.7 include barium sulfate (refractive index: 1.65), talc (refractive index: 1.54 to 59), magnesium carbonate (refractive index: 1.57-1.60), and clay (refractive index: 1.55-1.57). Alumina (refractive index: 1.65), aluminum hydroxide (refractive index: 1.65), diaspore (refractive index: 1.62-1.65), mica powder (refractive index: 1.59), hydrotalcite (refractive index: 1.50), Slaked lime (refractive index: 1.55), calcium hydroxide (refractive index: 1.57), calcium carbonate (refractive index: 1.58), calcium sulfate (refractive index: 1.59), potassium carbonate (refractive index: 1.5), and the like.

The organic filler may, for example, be polyethylene, polypropylene, polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate, crosslinked polymethyl methacrylate, or the like. Co-polymerization of butyl methacrylate, polyimide, polyamine, polyester, polyvinyl chloride, polyposition Dichloroethylene, polydivinylbenzene, fluororesin, polyphenylene ether, polyphenylene sulfide, polymethylpentene, urea resin, melamine resin, benzoguanamine resin, polyacetal resin, furan resin, polyoxyl For the resin, the epoxy resin cured product, etc., polyethylene, polypropylene, cross-linked polymethyl methacrylate, cross-linked polybutyl methacrylate or the like can be preferably used.

The organic filler having a refractive index of less than 1.5 may, for example, be a methyl methacrylate resin (refractive index: 1.49), polymethyl methacrylate (refractive index: 1.49), vinyl acetate resin (refractive index: 1.46), or polyoxyl Resin (refractive index: 1.43), polyacetal resin (refractive index: 1.48), polypropylene resin (refractive index: 1.48), and the like. The organic filler having a refractive index of more than 1.7 is exemplified by a resin for a polythiourethane-based optical material (refractive index: 1.75). The organic filler having a refractive index of 1.5 to 1.7 may, for example, be a melamine resin (refractive index: 1.6), a nylon (refractive index: 1.53), a polystyrene (refractive index: 1.6), a polyethylene (refractive index: 1.53), or a partial Dichloroethylene resin (refractive index: 1.61), polycarbonate (refractive index: 1.59), and the like.

The refractive index of the filler can be measured by the Beck line method. The method comprises placing the filler component in the immersion liquid, dropping it onto the glass slide, covering the cover glass, and observing the Beck line visible at the interface between the filler and the immersion liquid with a microscope with a small aperture to obtain the same refractive index as the filler. The immersion liquid can measure the refractive index.

Further, since the filler can be blended with higher filling, it is preferable that the filler having the slurry state has a primary particle diameter of 1 μm or less, so that the filler can be blended with higher filling. The lower limit is preferably 0.005 μm or more.

The filler having a primary particle diameter of 1 μm or less may, for example, be SO-E1 (primary particle diameter: 0.25 μm), SO-E 2 (primary particle diameter: 0.5 μm), SO- E3 (primary particle size: 1.0 μm) such as cerium oxide (all manufactured by Admatechs), B-30 (primary particle size: 0.3 μm), B-31 (primary particle size: 0.3 μm), B-33 ( Primary particle size: 0.3μm), BF-10 (primary particle size: 0.06μm), BF-1 (primary particle size: 0.05μm), BF-20 (primary particle size: 0.03μm), BF-40 (primary particle) Barium sulfate (manufactured by Nippon Chemical Co., Ltd.), Higilite H42 (primary particle size: 1 μm), H42M (primary particle size: 1 μm), and H43 (primary particle size: 0.75 μm), the same diameter: 0.01 μm) Aluminum hydroxide (manufactured by Showa Denko Co., Ltd.) such as H43M (primary particle diameter: 0.75 μm), DHT-4A (primary particle diameter: 0.4 μm), DHT-4A-2 (primary particle diameter: 0.4 μm), DHT Hydrotalcite (manufactured by Kyowa Chemical Co., Ltd.) such as -4C (primary particle diameter: 0.4 μm) and DHT-4H (primary particle diameter: 0.4 μm). Among these, in particular, in the case where the particle diameter is extremely small and the powder is easily aggregated, barium sulfate is preferred.

The total amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, even more preferably 0.1 to 150 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the blending amount of the filler is 500 parts by mass or less, the viscosity of the photocurable resin composition does not become excessively high, and the printability is good, and the cured product is less likely to become brittle.

(photoreactive monomer)

The photocurable resin composition of the present invention preferably contains a photoreactive monomer. A compound having one or more ethylenically unsaturated groups in a photoreactive single-system molecule. The photoreactive single system assists the photohardener of the carboxyl group-containing resin by irradiation with active energy rays.

As the photoreactive monomer, a known photoreactive monomer can be used. For example, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, (methyl) Epoxy acrylate and the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; and glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol. Acrylates; N,N-dimethyl decylamine, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide, etc.; propylene amide; N, N-II Aminoalkyl acrylate such as methylaminoethyl acrylate or N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, gin-hydroxyl a polyhydric alcohol such as an ethyl tripolyisocyanate or a polyacrylate such as an ethylene oxide adduct, a propylene oxide adduct or an ε -caprolactone adduct; a phenoxy acrylate; Dihydric acrylates such as bisphenol A diacrylate, and ethylene oxide adducts of such phenols or propylene oxide adducts; glycerol diglycidyl ether, glycerol triglycidyl ether, trishydroxyl a polyacrylate of a glycidyl ether such as a propane triglycidyl ether or a triglycidyl tripolyisocyanate; not limited to the foregoing An acrylic acid obtained by directly acrylating a polyhydric alcohol, a polycarbonate diol, a hydroxyl terminated polybutadiene, a polyester polyol, or the like, or urethane acrylated by a diisocyanate At least one of an ester and a melamine acrylate, and each methacrylate corresponding to the above acrylate.

Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin or a hydroxy acrylate such as pentaerythritol triacrylate may be used. And a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate, an epoxy group urethane acrylate compound obtained by reacting a hydroxyl group of the epoxy acrylate resin, etc., as a photoreactive single body. Such an acryl epoxy resin can improve photocurability without lowering the dryness of the finger touch.

The blending amount of the compound having an ethylenically unsaturated group in the molecule used as the photoreactive monomer is preferably 5 to 100 parts by mass, more preferably 5 to 70, based on 100 parts by mass of the resin containing a carboxyl group. The proportion of the mass. When the blending amount is 5 parts by mass or more, the photocurability of the photocurable resin composition is good. On the other hand, when it is 100 mass parts or less, the coating film is not easily 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. The thermosetting component may be an amine resin, an isocyanate compound, a blocked isocyanate compound, a maleimide compound, a benzoxazine compound, an oxazoline compound, a carbodiimide compound, a cyclic carbonate compound, or a polyfunctional compound. A known thermosetting resin such as an oxetane compound, an episulfide resin, or an epoxy resin.

The amine-based resin may, for example, be an amine-based resin such as a melamine derivative or a benzoguanamine derivative. For example, there are a methylol melamine compound, a methylol benzoguanamine compound, a methylol acetylene urea compound, a methylol urea compound, and the like. Further, alkoxymethylated melamine complex , alkoxymethylated benzoguanamine compound, alkoxymethylated acetylene urea compound and alkoxymethylated urea compound by using the respective methylol melamine compound, methylol benzoate The hydroxymethyl group of a guanamine compound, a methylol acetylene urea compound, and a methylol urea compound is converted into an alkoxymethyl group. The type 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 formaldehyde concentration of 0.2% or less which is good for the human body or the environment is preferable.

Commercial products of the above-mentioned amine-based resin include, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, and 202. Same as 1156, the same 1158, the same 1123, the same 1170, the same 1174, the same UFR65, the same 300 (above, Mitsui Cyanamid company), NIKALAC Mx-750, the same Mx-032, the same Mx-270, the same Mx-280, Same as Mx-290, same Mx-706, same Mx-708, same Mx-40, same Mx-31, same Ms-11, same Mw-30, same Mw-30HM, same Mw-390, same Mw-100LM, Same as Mw-750LM, (above, Sanwa Chemical Co., Ltd.).

As the above isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-methylphenylene diisocyanate, 2,6-methylphenylene diisocyanate, and naphthalene-1,5- Diisocyanate, o-dimethylphenylene diisocyanate, m-dimethylphenylene diisocyanate and 2,4-methylbenzene Base dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylene double (ring). Hexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Further, an adduct body, a biuret body, and a trimeric isocyanate body of the above-exemplified isocyanate compound may be mentioned.

The blocked isocyanate group contained in the blocked isocyanate compound protects the isocyanate group by a reaction with a blocking agent, and is temporarily inactivated. Upon heating to the specified temperature, the capping agent will dissociate to form an isocyanate group.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound which can be reacted with the blocking agent include a trimeric isocyanate type, a biuret type, and an adduct type. The isocyanate compound used for the synthesis of the blocked isocyanate compound may, for example, be an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate, and the alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate blocking agent include phenolic terminal blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; ε-caprolactam, δ-valeroinamide, and γ-butane An internal amide-based blocking agent such as guanamine or β-propionalamine; an active methylene-based blocking agent such as ethyl acetate and acetonitrile; methanol, ethanol, propanol, butanol, and pentyl Alcohol, ethylene glycol monomethyl ether, ethylene Alcohol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate And an alcohol-based terminal blocking agent such as ethyl lactate; a hydrazine blocking agent such as formaldehyde hydrazine, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, diethyl hydrazine mono oxime or cyclohexane hydrazine; a mercaptan blocking agent such as mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl mercaptan or ethyl thiophenol; acid amide amine such as decylamine or benzoguanamine Terminal agent; quinone imine capping agent such as succinic acid succinimide and succinimide maleate; amine blocking agent such as xylyleneamine, aniline, butylamine, dibutylamine, etc.; imidazole, 2 - an imidazole-based blocking agent such as ethyl imidazole; an imide-based blocking agent such as methyleneimine or acrylimine.

The blocked isocyanate compound may be a commercially available one, and examples thereof include Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayeramide Co., Ltd., trade name), CORONATE 2512, CORONATE 2513, CORONATE 2520 (above, manufactured by Japan Polyurethane Industrial Co., Ltd., trade name), B-830, B -815, B-846, B-870, B-874, B-882 (above, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name), TPA-B80E, 17B-60PX, E402-B80T (above, manufactured by Asahi Kasei Chemicals Co., Ltd.) , product name) and so on. Further, Sumidur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a terminal blocking agent.

The blending amount of the polyisocyanate compound or the blocked isocyanate compound is preferably from 1 to 100 parts by mass, more preferably from 2 to 70 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. The aforementioned blending amount is When the amount is 1 part by mass or more, the toughness of the coating film can be sufficiently obtained. On the other hand, when it is 100 mass parts or less, the fall of storage stability can be suppressed.

In the photocurable resin composition of the present invention, a urethane-based catalyst can be further added. The urethane-based catalyst is preferably one or more amines selected from the group consisting of tin-based catalysts, metal chlorides, metal acetoacetates, metal sulfates, amine compounds, and amine salts. Carbamate catalyst.

The tin-based catalyst may, for example, be an organotin compound such as stannous octoate or dibutyltin dilaurate or an inorganic tin compound.

The metal chloride is a chloride selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include cobalt (III) chloride, nickel (II) chloride, and chlorination. Iron (III) and the like.

The metal acetoacetate is an acetoacetate selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al, and examples thereof include cobalt acetylacetonate and acetylpyruvate. Nickel, acetonitrile pyruvate and the like.

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

Examples of the maleidinium compound include a polyfunctional aliphatic/alicyclic maleimide and a polyfunctional aromatic maleimide. As a polyfunctional aliphatic/alicyclic maleimide, for example, N,N'-methylene bismaleimide, N,N'-extended ethyl bismaleimide, ginseng (Hydroxyethyl)trimeric isocyanate and aliphatic/alicyclic maleic imide carboxylic acid dehydrated ester The maleic imidate compound of the trimeric isocyanate skeleton, the amide (urethane hexyl) trimeric isocyanate and the aliphatic/alicyclic maleimide alcohol are esterified with a trimeric isocyanate skeleton of a trimeric isocyanate skeleton, such as a maleic acid imine carbamate compound, a polymaleimide group; an isophorone bis-carbamate double (N-ethyl horse) Deuterated imine), triethylene glycol bis (maleimide ethyl carbonate), dehydratization of aliphatic/alicyclic maleic imine carboxylic acid with various aliphatic/alicyclic polyols Or an aliphatic/alicyclic polymaleimide compound obtained by transesterifying an aliphatic/alicyclic maleimide carboxylate with various aliphatic/alicyclic polyols; An aliphatic/alicyclic polymaleimide compound obtained by ether-opening an aliphatic/alicyclic maleic imine carboxylic acid with various aliphatic/alicyclic polyepoxides, Aliphatic/alicyclic polymaleide obtained by subjecting aliphatic/alicyclic maleimide to various aliphatic/alicyclic polyisocyanates Amine compounds such as urethane.

Polyfunctional aromatic maleimide, such as dehydration and esterification of maleic imine carboxylic acid with various aromatic polyols, or transesterification of maleic imine carboxylate with various aromatic polyols An aromatic polymaleimide compound obtained by subjecting an aromatic polymaleimide compound to an ether ring-opening reaction of a maleimide carboxylic acid and various aromatic polyepoxides Aromatic polyfunctional maleimide of aromatic polymaleimide urethane compound obtained by subjecting maleic iminol to various aromatic polyisocyanates for urethanation reaction Classes, etc.

Specific examples of polyfunctional aromatic maleimide can be listed For example, N, N'-(4,4'-diphenylmethane) bismaleimide, N,N'-2,4-methylphenylene bismaleimide, N,N'- 2,6-methylphenylene bismaleimide, 1-methyl-2,4-bismaleimide benzene, N,N'-m-phenylene bismaleimide, N , N'-p-phenylene bismaleimide, N,N'-m-stilbene bismaleimide, N,N'-4,4'-stranded biphenyl Yttrium, N, N'-4, 4'-[3,3'-dimethyl-extended biphenyl] bismaleimide, N, N'-4, 4'-[3, 3 '-Dimethyldiphenylmethane]Bismaleimide, N,N'-4,4'-[3,3'-diethyldiphenylmethane]Bismaleimide, N, N'-4,4'-diphenylmethane bismaleimide, N,N'-4,4'-diphenylpropane bismaleimide, N,N'-4,4'- Diphenyl ether bismaleimide, N,N'-3,3'-diphenylfluorene bismaleimide, N,N'-4,4'-diphenylfluorene double mala Imine, 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-t-butyl-4-(4-malian) Amine phenoxy)phenyl]propane, 2,2-bis[3-s-butyl-4-(4-maleimidophenoxy)phenyl]propane 1,1-bis[4-(4-maleimidophenoxy)phenyl]decane, 1,1-bis[2-methyl-4-(4-maleimide phenoxy) 5-)-t-butylphenyl]-2-methylpropane, 4,4'-cyclohexylene-bis[1-(4-maleimidophenoxy)-2-(1, 1-dimethylethyl)benzene], 4,4'-methylene-bis[1-(4-maleimidophenoxy)-2,6-bis(1,1-dimethyl Ethyl)benzene], 4,4'-methylene-bis[1-(4-maleimidophenoxy)-2,6-di-s-butylbenzene], 4,4'- Cyclohexylene-bis[1-(4-maleimidophenoxy)-2-cyclohexylbenzene, 4,4'-methylenebis[1-(maleimide phenoxy)- 2-mercaptobenzene], 4,4'-(1-methylethylidene)-bis[1-(maleimide phenoxy)-2,6-bis(1,1-dimethyl Ethyl)benzene, 4,4'-(2-ethylhexylene)-bis[1-(maleimide phenoxy)-benzene], 4,4'-(1-methylglycol base)- Bis[1-(maleimide phenoxy)-benzene], 4,4'-cyclohexylene-bis[1-(maleimidophenoxy)-3-methylbenzene], 2 ,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-methyl-4-(4-maleimide phenoxy) Phenyl]propane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3,5-dimethyl 4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3,5-dimethyl-4-(4-maleimide phenoxy)benzene Hexafluoropropane, 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-ethyl-4-( 4-maleimide phenoxy)phenyl]hexafluoropropane, bis[3-methyl-(4-maleimidophenoxy)phenyl]methane, bis[3,5-dimethyl Base-(4-maleimidophenoxy)phenyl]methane, bis[3-ethyl-(4-maleimidophenoxy)phenyl]methane, 3,8-bis[4 -(4-maleimide phenoxy)phenyl]-tricyclo[5.2.1.02,6]decane, 4,8-bis[4-(4-maleimidophenoxy)benzene Base]-tricyclo[5.2.1.02,6]decane, 3,9-bis[4-(4-maleimide phenoxy) Phenyl]-tricyclo[5.2.1.02,6]decane, 4,9-bis[4-(4-maleimidophenoxy)phenyl]-tricyclo[5.2.1.02,6]癸Alkane, 1,8-bis[4-(4-maleimidophenoxy)phenyl]menthane, 1,8-bis[3-methyl-4-(4-maleimide benzene) Oxy)phenyl]menthane, 1,8-bis[3,5-dimethyl-4-(4-maleimidophenoxy)phenyl]mentane, and the like.

Commercial products of the aforementioned maleic imine compound include, for example, BMI-1000, BMI-1000H, BMI-1000S, BMI-1100, BMI-1100H, BMI-2000, BMI-2300, BMI-3000, BMI-3000H. , BMI-4000, BMI-5100, BMI-7000, BMI-7000H, and BMI-TMH (above, Daiwa Kasei Kogyo Co., Ltd.), MIA-200 (DIC) Company system) and so on.

These bismaleimide derivatives can be synthesized by a general method or a commercially available product. In particular, among the bismaleimide derivatives, those which do not contain a halogen atom in the molecule are preferred from the viewpoint of not causing a load on the environment. These may be used alone 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. For the commercial products, "F-a" (manufactured by Shikoku Chemicals Co., Ltd.) can be cited.

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

Examples of the carbodiimide compound include dicyclohexylcarbodiimide and diisopropylcarbodiimide.

The cyclic carbonate compound is not particularly limited as long as it is a cyclic compound and has a carbonate bond. As an example, a alkyl carbonate compound having a polyfunctional structure can be cited.

The above polyfunctional oxetane compound, except bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxa) Cyclobutane methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3) -ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, acrylic acid (3-ethyl-3-oxygen) Heterocyclobutane methyl ester, methacrylic acid (3-A) Methyl-3-oxetanyl)methyl ester, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional oxalate of such oligomers or copolymers Examples of the cyclobutanes include oxetane and novolak resins, poly(p-hydroxystyrene), Cardo type bisphenols, calixarene, resorcinol calixarene, or sesquiterpene. An etherified product of a resin having a hydroxyl group such as oxyalkylene. Other examples thereof include a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate.

Examples of the above-mentioned episulfide resin include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation, and YSLV-120TE manufactured by Tosho Kasei Co., Ltd., and the like. Further, an episulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by using the same synthesis method may be used.

As the epoxy resin, a conventionally known polyfunctional 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 a solid or semi-solid.

Examples of the epoxy resin include jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840 manufactured by DIC Corporation, Epiclon 850, Epiclon 1050, Epiclon 2055, and Epotohto YD-011, YD-013, and YD manufactured by Tosho Kasei Co., Ltd. -127, YD-128, DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei, manufactured by Sumitomo Chemical Industries, Ltd. Industrial company AER330, AER331, AER661, AER664, etc. (all are trade names) of bisphenol A epoxy resin; Mitsubishi Chemical JERYL903 manufactured by the company, Epiclon 152, Epiclon 165 manufactured by DIC Corporation, Epotohto YDB-400 manufactured by Dongdu Chemical Co., Ltd., YDB-500, DER542 manufactured by Dow Chemical Co., Ltd., Sumi-Epoxy ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd. ESB-700, AER711, AER714, etc. (both trade names) made of brominated epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; jER152, jER154, manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438, DIC manufactured by Dow Chemical Co., Ltd. Epiclon N-730, Epiclon N-770, Epiclon N-865, Epotohto YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020 manufactured by Nippon Kayaku Co., Ltd. EOCN-104S, RE-306, NC-3000, Sumi-Epoxy ESCN-195X manufactured by Sumitomo Chemical Industries, Inc., ESCN-220, AERECN-235, ECN-299, manufactured by Asahi Kasei Kogyo Co., Ltd., manufactured by Nippon Steel Chemical Co., Ltd. YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A, DIC company Epiclon N-680, N-690, Novolac type epoxy resin such as N-695 (all trade names); Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Dongdu Epotohto YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F-type epoxy resin manufactured by Chemical Company; Epotohto ST-2004, ST-2007, ST-3000 manufactured by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A epoxy resin (product name); JER604 manufactured by Mitsubishi Chemical Corporation, Epotohto YH-434 manufactured by Tosho Chemical Co., Ltd., Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. Glycidylamine type epoxy resin; B-uret urea type epoxy resin; Daicelization Ethylene ring epoxy resin of Celloxide 2021 (all trade name) manufactured by Industrial Co., Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN manufactured by Dow Chemical Co., Ltd., EPPN-501, EPPN-502, etc. Name) trihydroxyphenylmethane type epoxy resin; dimethyl hydroxy phenol type or bisphenol type epoxy resin such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation Such a mixture; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation; jER157S manufactured by Mitsubishi Chemical Corporation Bisphenol A novolac type epoxy resin, etc.; tetraphenol ethane type epoxy resin manufactured by Mitsubishi Chemical Corporation, jERYL-931 (both trade names); TEPIC manufactured by Nissan Chemical Industries Co., Ltd. a heterocyclic epoxy resin of the trade name; a diglycidyl phthalate resin such as Blemmer DGT manufactured by Nippon Oil Co., Ltd.; and a tetraglycidyl xylylene ethane hydride resin such as ZX-1063 manufactured by Tosho Chemical Co., Ltd. ESN-190, ESN-360, manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700, etc. An epoxy resin having a naphthyl group; an epoxy resin having a dicyclopentadiene skeleton such as HP-7200 or HP-7200H manufactured by DIC Corporation; and a glycidol methacrylate such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Ester copolymer epoxy resin; further copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; CTBN modified epoxy resin (for example, YR-102, YR-450 manufactured by Dongdu Chemical Co., Ltd.) Etc. etc., but not limited to this. Among these, a bisphenol A type epoxy resin, a naphthalene type epoxy resin, a phenol novolak type epoxy resin, a 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 thermosetting component is contained, it is preferred to further contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl Imidazole derivatives such as 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-( Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine An amine compound such as an amine compound, diterpene adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like. In addition, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (trade names of all imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., and U-CAT (registered by San-Apro Co., Ltd.) can be cited. Trademarks) 3503N, U-CAT3502T (both trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (both bicyclic oxime compounds and salts thereof). It is not particularly limited thereto, and it is only required to promote a thermosetting catalyst of an epoxy resin or an oxetane compound or a reaction of at least one of an epoxy group and an oxetanyl group with a carboxyl group. These may be used alone or in combination of two or more. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2 can also be used. , 4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Trimeric isocyanate Compound, 2,4-diamino-6-methacryloxyethyl-S-triazine. The S-triazine derivative such as a trimeric isocyanate addition product is preferably used in combination with the above-mentioned thermosetting catalyst, which also has a function of the adhesion imparting agent.

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, per 100 parts by mass of the thermosetting component.

(Colorant)

The photocurable resin composition of the present invention can be blended with a colorant. As the coloring agent, a conventionally known coloring agent such as red, blue, green, or yellow may be used, and a pigment, a dye, or a coloring matter may be used. Specifically, the number with the color index (C.I.; The Society of Dyers and Colourists) is listed. However, from the viewpoint of a reduction in environmental load and influence on the human body, a coloring agent containing no halogen is preferred.

Red colorant:

Examples of the red coloring agent include a monoazo type, a disazo type, an azo lake type, a benzimidazolone type, an anthraquinone type, a pyrrolopyrroledione type, a condensed azo type, an anthraquinone type, and a quinacridone. Department and so on.

Blue colorant:

The blue coloring agent is a phthalocyanine or an anthraquinone type, and the pigment system is a compound classified as a pigment, and a metal-substituted or unsubstituted phthalocyanine compound may be used.

Green colorant:

The green colorant is similarly phthalocyanine, lanthanide or lanthanide, and a metal-substituted or unsubstituted phthalocyanine compound may be used.

Yellow colorant:

Examples of the yellow coloring agent include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, and an anthraquinone type.

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

(Organic solvents)

In the photocurable resin composition described above, in order to prepare a resin composition or to prepare a filler into a slurry state, an organic solvent may be used in order to adjust the viscosity applied to the substrate or the carrier film.

Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents, and the like. More specifically, it is a ketone such as methyl ethyl ketone or cyclohexanone; an aromatic hydrocarbon such as toluene, xylene or tetramethylbenzene; celecoxib, methyl acesulfame, and butyl oxime Glycols such as sulphate, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Ethers; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate (carbitol acetate), dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol base Esters such as ether acetate, propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum ether, petroleum brain, hydrogenation Petroleum solvent such as petroleum brain, solvent petroleum brain, etc. These organic solvents may be used singly or in combination of two or more.

(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 as needed. These can be used in the art of electronic materials. Further, in the photocurable resin composition of the present invention, a known conventional tackifier such as fine powder of ceria, hydrotalcite, organic bentonite or montmorillonite may be blended; polyfluorene, fluorine or polymer At least one of an antifoaming agent and a leveling agent; a decane coupling agent such as an imidazole type, a thiazole type or a triazole type; and a conventionally known additive such as a rust preventive agent.

The photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method by the organic solvent, for example, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, or the like. A method such as a screen printing method or a curtain coating method is applied to a substrate, and the organic solvent contained in the composition can be volatilized and dried (temporary drying) at a temperature of about 60 to 100 ° C to form a non-sticky layer ( Tackfree) coating.

The substrate is not limited to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, and paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/ Do not Fiber cloth epoxy resin, glass cloth / paper epoxy resin, synthetic fiber epoxy resin, fluorine. Polyethylene. PPO (polyphenylene ether, polyoxymethylene). A high-temperature circuit such as a cyanate ester is made of a copper-clad laminate or the like, and is a copper-clad laminate of all grades (FR-4, etc.), another polyimide film, a PET film, or a glass substrate. , ceramic substrates, wafer boards, etc.

The photocurable resin composition of the present invention may be applied to a film (hereinafter also referred to as a carrier film) to form a dry film. In the case of dry film formation, the photocurable resin composition of the present invention is diluted with the organic solvent to adjust the viscosity to a suitable viscosity, and is used as a comma coater, a knife coater, a lip applicator, A rod coater, a squeeze coater, a reverse coater, a transfer roll coater, a gravure coater, and a spray coater are coated to a uniform thickness on the carrier film, usually The film was dried by drying at a temperature of 50 to 130 ° C for 1 to 30 minutes. The coating film thickness is not particularly limited, and is generally selected in the range of 5 to 150 μm, preferably 10 to 60 μm, in terms of film thickness after drying.

The carrier film is a plastic film, preferably a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like. Plastic film. The thickness of the carrier film is not particularly limited, and is generally selected in the range of 5 to 150 μm. It is preferably in the range of 10 to 150 μm.

After the photocurable resin composition of the present invention is formed on the carrier film, it is preferable to further laminate the peelable coating film on the surface of the film for the purpose of preventing dust from adhering to the surface of the film.

As the peelable coating film, for example, a polyethylene film or a polyethylene can be used. When the coated film is peeled off from the tetrafluoroethylene film, the polypropylene film, the surface-treated paper, or the like, the adhesion between the film and the coated film may be smaller than the adhesion between the film and the carrier film.

After the dry film of the present invention is bonded to the substrate by contact with the substrate by a laminator or the like, the carrier film is peeled off to form a resin insulating layer.

The volatilization drying of the photocurable resin composition of the present invention after coating on a substrate or a carrier film can be carried out using a hot air circulating drying oven, an IR furnace, a heating plate, a convection oven, etc. The heat source of the air heating method is performed by a method in which the hot air in the dryer is countercurrently contacted and a method in which the nozzle blows the support.

By coating the photocurable resin composition of the present invention, the coating film or the dry film obtained by volatilizing the solvent is exposed to light (active energy ray irradiation), and the exposed portion (the portion irradiated with the active energy ray) is hardened. . Further, by contact (or non-contact method), direct pattern exposure is selectively performed by an exposure or laser direct exposure machine through a photomask formed with a pattern, and the unexposed portion is diluted with a base. An aqueous solution (for example, 0.3 to 3 wt% sodium carbonate solution) is developed to form a resist pattern. Patterns can also be formed by laser processing as needed.

The exposure machine used for the active energy ray irradiation may be a device that emits ultraviolet rays in the range of 350 to 450 nm, as long as it is equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like. A rendering device (for example, a laser direct imaging device that directly renders an image with a laser by CAD data from a computer). For laser light sources of direct-drawing machines, gas lasers and solid lasers can be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, and is generally in the range of 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and the developing solution may be a base such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, ammonia or an amine. Aqueous solution.

The method for producing a printed wiring board according to the present invention is characterized in that it comprises a step of mixing two or more types of fillers having different refractive indices, and using one or more types of fillers as a powder and one or more kinds of fillers in a slurry state. . As described above, the particle size distribution of the photocurable resin composition is preferably D ₅₀ of 3.0 μm or less and D ₉₀ of 8.0 μm or less. Further, among the two or more types of fillers, one or more kinds of fillers preferably have a refractive index of less than 1.5 or more than 1.7 and are blended in a slurry state. Among the above two or more types of fillers, one or more types of fillers preferably have a refractive index of 1.5 to 1.7 and are blended with a powder. The materials used in the method for producing a printed wiring board of the present invention are as described above.

[Examples]

Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is of course not limited to the following examples. In addition, the following "Parts" and "%" are quality benchmarks unless otherwise specified.

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

In a high-temperature autoclave equipped with a thermometer, a nitrogen gas introducing device, an alkylene oxide introducing device, and a stirring device, 119.4 g of a novolac type cresol resin (Shonol CRG951, OH equivalent: 119.4) and potassium hydroxide were placed. 1.19 g and 119.4 g of toluene were subjected to nitrogen substitution in the system while stirring, and the temperature was raised by heating. Then, 63.8 g of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C and 0 to 4.8 kg/cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy resin of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl group value of 182.2 g/eq. Propane reaction solution. This is a phenolic hydroxyl group which is added to an average of 1.08 moles of alkylene oxide per equivalent. 293.0 g of an 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 placed in a mixer, a thermometer, and an air blowing tube. In the reactor, air was blown at a rate of 10 ml/min while stirring at 110 ° C for 12 hours. The water formed by the reaction was used as an azeotropic mixture with toluene to distill off 12.6 g of water. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, followed by water washing. Thereafter, toluene was substituted with 118.1 g of diethylene glycol monoethyl ether acetate (carbitol acetate) in an evaporator, and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 g of the obtained novolac type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min. While stirring, 60.8 g of tetrahydrophthalic anhydride was slowly added, and the mixture was reacted at 95 to 101 ° C for 6 hours. A carboxyl group-containing resin having a solid acid value of 88 mgKOH/g and a solid content of 71% was obtained. This was taken as the resin solution A-1.

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

An o-cresol novolac type epoxy resin (made by DIC, EPICLON N-695, softening point 95 ° C, epoxy) was placed in 600 g of diethylene glycol monoethyl ether acetate (carbitol acetate). The base equivalent of 214, the average functional group number of 7.6), 1070 g, 360 g of acrylic acid, and 1.5 g of hydroquinone were heated and stirred at 100 ° C to uniformly dissolve. Next, 4.3 g of triphenylphosphine was placed, and the mixture was heated to 110 ° C for 2 hours, and then heated to 120 ° C for further 12 hours. Into the obtained reaction liquid, 415 g of an aromatic hydrocarbon (Solvesso 150) and 456.0 g of tetrahydrophthalic anhydride were placed, and the reaction was carried out at 110 ° C for 4 hours, and after cooling, a solid content acid value of 89 mg KOH / g and a solid content were obtained. 65% of a resin containing a carboxyl group. This was used as the resin solution A-2.

(evaluation of refractive index)

The refractive index of the resin (solid content) of the resin solutions A-1 and A-2 obtained above was measured at 589.3 nm and 25 ° C using a refractometer ER-7MW manufactured by ERMA. The results are shown together with the refractive indices of cerium oxide, aluminum oxide, barium sulfate, and hydrotalcite in Table 1 below.

(modulation of cerium oxide slurry)

700 g of normal spherical cerium oxide (SO-E2 manufactured by Admatech Co., Ltd.), 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and vinyl decane as a decane coupling agent 5 g of the mixture was mixed and stirred, and dispersed in a bead mill using 0.5 μm of zirconia beads. This was repeated three times to prepare a cerium oxide slurry filtered through a 3 μm filter membrane.

(modulation 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 dispersing agent were mixed and stirred, and beads were obtained in the same manner as above. The mill is subjected to dispersion treatment. This was repeated three times to prepare an alumina slurry filtered through a 3 μm filter membrane.

(modulation of barium sulfate slurry)

700 g of barium sulfate (B-30 manufactured by Dai Chemical Industry Co., Ltd.) as a solvent 295 g of diethylene glycol monoethyl ether acetate (carbitol acetate) and 5 g of a wet dispersing agent were mixed and stirred, and dispersed in a bead mill in the same manner as above. This was repeated three times to prepare a barium sulfate slurry filtered through a 3 μm filter membrane.

(modulation 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 dispersing agent were mixed and stirred, and the same as above. Dispersion treatment was carried out in a bead mill. This was repeated three times to prepare a hydrotalcite slurry filtered through a 3 μm filter membrane.

<Examples 1 to 5 and Comparative Examples 1 to 4>

The above resin solution and slurry were blended with the blending (parts by mass) shown in Table 2, premixed with a stirrer, and kneaded by a 3-roll mill to prepare Examples 1 to 5 and Comparative Examples 1 to 4. Photocurable resin composition.

In addition, the degree of dispersion of the obtained photocurable resin composition was evaluated by particle size measurement by a grind meter manufactured by Erichsen Co., Ltd., and each was 15 μm or less.

The meanings of the respective supplementary numerals in the foregoing Table 2 are as follows.

*1: SO-E2 manufactured by Admatech

*2: ASFP-20 made by Denka

*3: B-30 manufactured by 堺Chemical Industries

*4: DHT-4A manufactured by Concord Chemical Industries Co., Ltd.

*5: dipentaerythritol hexaacrylate

*6: Phenolic novolac type epoxy resin

*7: Triglycidyl trimeric isocyanate

*8: Melamine

*9: 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide

*10: Pigment Blue 15:3

*11: Pigment Yellow 147

*12: Polyoxane defoamer

*13: Dipropylene glycol monomethyl ether

(Particle size distribution)

The particle size distribution of the photocurable resin composition of the above Example 3 and Comparative Example 2 was measured with a microtracker (MT3300EX, manufactured by Nikkiso Co., Ltd.). The results of Example 3 are shown in Figure 1 and the results of Comparative Example 2 are shown in Figure 2. The D ₅₀ of Example 3 was 0.41 μm and the D ₉₀ was 1.7 μm. Comparative Example 2 had a D ₅₀ of 3.7 μm and a D ₉₀ of 8.1 μm.

Characteristic evaluation:

The photocurable resin composition of each of the above examples and comparative examples was applied by screen printing on a copper foil substrate formed by patterning, dried in a hot air circulating drying oven at 80 ° C for 30 minutes, and then allowed to cool to The evaluation substrate was obtained at room temperature. For the obtained evaluation substrate, characteristics were evaluated as follows.

In the following evaluation, the pattern of the photocurable resin composition was formed, and the obtained evaluation substrate was subjected to an exposure apparatus equipped with a high-pressure mercury lamp (an exposure machine manufactured by ORC Manufacturing Co., Ltd. equipped with a mercury short-arc lamp). The exposure of the preferred exposure amount was carried out by developing at a temperature of 30 ° C, a spray pressure of 0.2 MPa, and a developing solution: a 1% by mass aqueous sodium carbonate solution for 60 seconds. The optimum exposure amount was exposed through a ladder plate (T4105C manufactured by Stouffer Co., Ltd.) during exposure, and the optimum exposure amount was obtained when the number of segments of the ladder plate remaining after development was 8 segments. After the formation of the pattern, the UV belt was irradiated with ultraviolet rays under the conditions of an accumulated exposure amount of 1000 mJ/cm ² , and then heated at 160 ° C for 60 minutes to cure the photocurable resin composition formed by the pattern.

(resolution)

For the evaluation substrate obtained, a negative pattern having a through hole opening diameter of 60 μm was used as a negative mask for resolution evaluation, and an opening pattern of the photocurable resin composition was formed under the above conditions and cured. The diameter of the bottom portion of the opening portion was observed and measured by a scanning electron microscope at 1000 times, and evaluated by the following evaluation conditions.

◎: diameter exceeds 55 μm, below 60 μm

○: diameter exceeding 50 μm, 55 μm or less

×: diameter less than 50 μm

(crack tolerance)

With respect to the obtained evaluation substrate, a negative pattern having four corners cut out was used as a negative mask for evaluation of resolution, and a pattern of a photocurable resin composition was formed under the above conditions and cured. After that, take -55 ° C for 30 minutes, 125 ° C for 30 minutes. 1 The heat history was applied cyclically, and after 1000 cycles, it was observed with an optical microscope and evaluated by the following evaluation conditions.

◎: no cracking occurred

○: Cracking occurred

×: Cracking occurred significantly

(HAST tolerance)

The same conditions as described above were evaluated except that a photocurable resin composition was applied to a BT substrate on which a comb-shaped electrode (line width/line pitch = 50 μm / 50 μm) was formed instead of the copper foil substrate on which the pattern was formed. Substrate. The photocurable resin composition on the obtained evaluation substrate was cured under the same conditions as above to form a cured coating film. The substrate obtained in this manner was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, and was energized at a voltage of 12 V for 168 hours in a tank HAST test. The insulation resistance value in the tank at 168 hours elapsed was evaluated in accordance with the following criteria.

◎: 10 ⁸ Ω or more

○: more than 10 ⁶ Ω is less than 10 ⁸ Ω

×: 10 ⁶ Ω or less

(haze value)

In each of Examples 1 to 5 and Comparative Examples 1 to 4, only the resin containing a carboxyl group in Table 2 and a filler component were mixed and applied to a glass substrate by an applicator, and a hot air circulating drying oven at 80 ° C was used. After drying for 30 minutes, a 25 μm thick dry coating film was obtained. UV-visible spectrophotometer (Japan spectrophotometer The company's V-600) measures the haze value of this dried coating film. The haze value = is expressed by the diffusion transmittance / total light transmittance × 100 (%), and the larger the value, the more the light is diffused. The smaller the haze value is, the less the light spreads, and therefore the resolution is excellent.

As is apparent from the results shown in the above Table 3, the photocurable resin composition of the present invention contains a plurality of fillers having different refractive indices, and a cured product having good resolution can be obtained. On the other hand, the photocurable resin composition shown in the comparative example has poor resolution, and the film formability is insufficient, and the performance as a photocurable resin composition is low.

Claims (10)

A photocurable resin composition comprising a carboxyl group-containing resin, a photopolymerization initiator, and a photocurable resin composition having two or more kinds of fillers having different refractive indices, which are characterized in that they are two or more kinds of Among the fillers, one or more kinds of fillers are blended in a powder, and one or more fillers are blended in a slurry state. The photocurable resin composition according to the first aspect of the invention, wherein the photocurable resin composition has a particle size distribution D ₅₀ of 3.0 μm or less and D ₉₀ of 8.0 μm or less. The photocurable resin composition of the first aspect of the invention, wherein one or more of the two or more kinds of 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 of the first aspect of the invention, wherein one or more of the two or more kinds of fillers have a refractive index of 1.5 to 1.7 and are mixed with a powder. The photocurable resin composition according to claim 1, wherein the carboxyl group-containing resin has an aromatic ring. The photocurable resin composition according to the first aspect of the invention, 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 of claim 1, which further comprises a photoreactive monomer. A dry film obtained by coating and drying a photocurable resin composition of the first aspect of the patent application on a film. A printed wiring board comprising: a photocurable resin composition according to claim 1 of claim 1 or at least one of an active energy ray irradiation and heating; or The cured product obtained by coating a photocurable resin composition on a film and drying it to obtain a cured product. A method for producing a photocurable resin composition comprising two or more kinds of fillers having different refractive indices, wherein one or more kinds of fillers are used as a powder, and one or more kinds of fillers are mixed in a slurry state. The steps.