KR20140111604A - Photocurable resin composition, dry film and cured product thereof, and printed wiring board having hardened coating film formed by using same - Google Patents

Abstract

The present invention relates to a photo-curable resin composition which is excellent in adhesiveness and flexibility with a substrate, has a low incidence of cracking and warpage of the cured product and can be developed by an aqueous alkali solution having excellent resolution, its photocurable dry film, And a printed wiring board comprising the same.
A photocurable resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a spherical silica filler having an average particle size of 300 nm or less, wherein the amount of the spherical silica filler (C) Curable resin composition, a photocurable dry film thereof, a cured product thereof, and a printed wiring board containing the same, wherein the amount of the photocurable resin composition is 60% by mass or more based on the total amount of the photocurable resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a photo-curable resin composition, a dry film and a cured product thereof, and a printed circuit board having a cured film formed using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a photo-curable resin composition which can be developed by an aqueous alkali solution, particularly a photo-curable resin composition for solder resists which is photo-cured by ultraviolet exposure or laser exposure, a dry film thereof and a cured product thereof and a cured film To a printed wiring board.

At present, some solder resists for printed wiring boards for civil use and most industrial printed wiring boards are subjected to ultraviolet light irradiation and then developed to form an image, from the viewpoints of high precision and high density, and are cured (finally cured) with at least one of heat and light irradiation. A liquid developing type solder resist is used.

Of these, alkali developing type photo-solder resists using an alkaline aqueous solution as a developer are mainly used in consideration of environmental problems, and they are used in large quantities in the production of actual printed wiring boards.

In such conventional alkali-developing type photo-solder resists, a carboxyl-containing resin, particularly an epoxy acrylate-modified resin, is generally used.

For example, Patent Document 1 discloses a solder resist composition containing a photosensitive resin, a photopolymerization initiator, a diluent, and an epoxy compound to which an acid anhydride is added to the reaction product of a novolac epoxy compound and an unsaturated monobasic acid.

Further, Patent Document 2 discloses a process for producing a polyurethane resin by adding (meth) acrylic acid to an epoxy resin obtained by reacting a reaction product of salicylaldehyde and monohydric phenol with epichlorohydrin and further reacting a polybasic carboxylic acid or an anhydride thereof A photosensitive resin, a photopolymerization initiator, an organic solvent, and the like.

Patent Document 3 discloses a polyurethane compound obtained by reacting an ethylenic unsaturated group and an epoxy acrylate compound having two or more hydroxyl groups, a diisocyanate compound and a diol compound having a carboxyl group, a polyurethane compound having an ethylenic unsaturated group, Discloses a photosensitive resin composition containing a monomer, a photopolymerization initiator, an epoxy compound, and a silica filler having an average particle size of 3 to 300 nm.

Japanese Patent Application Laid-Open No. 61-243869 (claims) Japanese Patent Laid-Open Publication No. Hei 3-250012 (Claims) Japanese Patent Application Laid-Open No. 2011-013622 (claims)

However, the conventional alkaline development type photo-solder resist ink is superior in durability, especially chemical resistance (for example, alkali resistance), water resistance, heat resistance, and adhesiveness to a substrate as compared with a thermosetting and solvent- There is still room for improvement.

This is considered to be attributable to the influence of the hydrophilic group-containing component which is the main component used for enabling the alkali development. That is, a chemical solution, water, water vapor, or the like is easily permeated by the hydrophilic group-containing component. This tends to lower the chemical resistance of the resist and the adhesion of the resist film and copper.

In addition, since the conventional alkaline development type photo solder resist ink has a large amount of shrinkage after curing and cooling and shrinking after curing, cracks and warpage of the coating film occur particularly at high temperature surface mounting in lead-free solder, . Particularly, filling of the solder resist ink with a filler may cause cracking of the coating film irrespective of the kind and the particle size thereof. Particularly, in the case of completing the coating, cracking of the coating film occurred remarkably.

Since the interposer substrate becomes thinner or coreless in the future, the solder resist for PKG is expected to require very good resolution.

Accordingly, an object of the present invention is to provide a photocurable resin composition which can overcome the above problems and is excellent in resolution, excellent in cold shock resistance and HAST resistance of a cured product, and capable of being developed by an alkali aqueous solution having a smaller warpage, A dry film, a cured product, and a printed wiring board comprising the same.

The above-

(A) an alkali-soluble resin,

(B) a photopolymerization initiator, and

(C) a spherical silica filler having an average particle diameter of 300 nm or less

(C) the amount of the spherical silica filler having an average particle diameter of 300 nm or less is 60 mass% or more based on the total amount of the photo-curable resin composition, wherein the photo-curable resin composition ≪ / RTI >

In the photocurable resin composition of the present invention, it is preferable that the alkali-soluble resin (A) is a carboxyl-containing resin having no photosensitive group (A-1).

It is preferable that the photocurable resin composition of the present invention further comprises a carboxyl group-containing resin having (A-2) photosensitive group as the (A) alkali-soluble resin.

The photocurable resin composition of the present invention preferably further contains (D) an epoxy resin.

In the photocurable resin composition of the present invention, it is preferable that the epoxy resin (D) is an epoxy resin having a (D-1) naphthalene structure.

In the photocurable resin composition of the present invention, it is preferable to use a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a polyalcohol resin in which a polyphenol compound is modified with an alkylene oxide as a carboxyl group-containing resin having no photosensitive group (A-1) desirable.

In the photo-curable resin composition of the present invention, (A-2) a photosensitive carboxyl group-containing resin, which is obtained by reacting a polyphenol compound with an alkylene oxide-modified polyalcohol resin with (meth) acrylic acid and further reacting a polybasic acid anhydride, Containing resin is preferably used.

In addition, the above object of the present invention can also be achieved by a photocurable dry film obtained by applying and drying a photocurable resin composition of the present invention to a carrier film, or a photocurable resin composition or a dry film obtained by applying the photocurable resin composition onto a carrier film, Or a printed circuit board having the cured product.

According to the present invention, there is provided a photocurable resin composition which can be developed by an aqueous alkali solution which is excellent in cold-shock resistance and HAST resistance of a dry film or a cured product, has a low incidence of warping of the cured product, A photocurable dry film, a cured product, and a printed wiring board comprising the same.

Particularly, in the present invention, since the silica filler having an average particle size of 300 nm is used, the silica filler is contemplated, whereby cracking is suppressed in the cured product, the resolution is improved and the warpability is lowered. In addition, the photocurable resin composition of the present invention can be cured even at a low exposure dose and is excellent in energy efficiency.

The photocurable resin composition of the present invention can be developed by an aqueous alkali solution,

(A) an alkali-soluble resin,

(B) a photopolymerization initiator, and

(C) a spherical silica filler having an average particle diameter of 300 nm or less

, And (C) the amount of the spherical silica filler having an average particle diameter of 300 nm or less is 60% by mass or more based on the total amount of the photocurable resin composition.

Each component will be described below.

[Component (A): alkali-soluble resin]

The present invention uses an alkali-soluble resin. As the alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. In particular, the use of a carboxyl group-containing resin is more preferable in view of developability.

As the carboxyl group-containing resin, conventionally known various carboxyl group-containing resins having a carboxyl group in the molecule and not having an ethylenically unsaturated double bond (non-photosensitive) or having (photosensitive) thereon can be used.

In particular, a non-photosensitive carboxyl group-containing resin having no ethylenically unsaturated double bond in the molecule is preferable in terms of improvement in flexibility, reduction in warpage (low warpability), and improvement in crack resistance.

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

(1) a dialcohol compound containing 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 polycarbonate-based polyol, a poly Containing urethane resin by a mid-chain reaction of a diol compound such as an ether-based polyol, a polyester-based polyol, a polyolefin-based polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(2) A urethane resin containing a carboxyl group by the reaction of a diisocyanate and a carboxyl group-containing dialcohol compound with a middle part.

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

(4) reacting a bifunctional epoxy resin or a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid, and reacting the produced hydroxyl group with phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride or the like Of a dibasic acid anhydride is added to the polyester resin.

(5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxetane resin, and reacting the resulting hydroxyl group with a polybasic acid anhydride.

(6) A polybasic acid anhydride is reacted with a reaction product such as a polyalcohol resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide Containing resin.

Further, in the present specification, (meth) acrylate means acrylate, methacrylate, and mixtures thereof.

As the non-photosensitive carboxyl group-containing resin, it is preferable to use the above-mentioned (1), (2), or (6) Among them, it is preferable to use the above-mentioned (6) which has an aromatic ring and is excellent in cold-shock resistance and PCT resistance, and has low warpage and good balance in all characteristics.

It is preferable to add a photosensitive carboxyl group-containing resin as the alkali-soluble resin to the resin composition of the present invention. Specific examples of the photosensitive carboxyl group-containing resin include the following compounds (any of oligomers and polymers). The ethylenically unsaturated double bond in the carboxyl group-containing resin is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

(7) a dialcohol compound containing 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 polycarbonate-based polyol, a poly A diol compound such as an ether type polyol, a polyester type polyol, a polyolefin type polyol, an acrylic type polyol, a bisphenol A type alkylene oxide adduct diol, a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group, Containing photosensitive urethane resin.

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

(9) In the synthesis of the resin of the above-mentioned (7) or (8), a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) (Meth) acrylated carboxyl group-containing photosensitive urethane resin.

(10) In the synthesis of the resin of the above-mentioned (8) or (9), one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acrylate obtained by adding a compound having a carboxyl group to a terminal (meth) acrylate.

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

(12) A photosensitive resin composition containing a carboxyl group-containing photosensitive resin, wherein a polybasic acid anhydride is added to the resulting hydroxyl group by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin .

(13) A process for producing a 2-functional oxetane resin, which comprises reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid, and reacting the resultant 2-hydroxyethyl phthalic acid, tetrahydrophthalic anhydride or hexahydrophthalic anhydride A carboxyl group-containing polyester photosensitive resin to which a basic acid anhydride is added.

(14) To a reaction product such as a polyalcohol resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound, with an alkylene oxide such as ethylene oxide or propylene oxide, Containing monocarboxylic acid, and further reacting the resultant reaction product with a polybasic acid anhydride to obtain a photosensitive resin containing a carboxyl group.

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

(16) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and at least one (meth) acryloyl group in one molecule to the above-mentioned resins (7) to (15).

These photosensitive carboxyl group-containing resins other than those described in (7) to (16) may be used alone, or they may be used alone or in combination of plural kinds. In particular, a resin having an aromatic ring in the carboxyl group-containing resin is preferable because it is excellent in resolution and has excellent PCT and crack resistance.

Among them, the carboxyl group-containing resin synthesized using a phenol compound as a starting material, such as the carboxyl group-containing resins (14) and (15), does not contain chlorine and therefore has excellent insulating properties such as HAST resistance and PCT resistance, In addition, the present invention can be preferably used because it is also excellent in toughness and, as a result, excellent in crack resistance.

The above-mentioned carboxyl group-containing resin, whether photosensitive or non-photosensitive, can be mentioned as follows.

That is, since a large number of carboxyl groups are present in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mg KOH / g, more preferably in the range of 45 to 120 mg KOH / g.

If the acid value of the carboxyl group-containing resin is less than 40 mgKOH / g, the alkali development becomes difficult. On the other hand, when the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, It is dissolved and peeled off as a developing solution without distinction between the light portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

The weight-average molecular weight of the above-mentioned carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight-average molecular weight is less than 2,000, the tackfree performance may deteriorate, the developability of the coated film after exposure can not be obtained, and the resolution may be significantly lowered. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated.

The compounding amount (solid content) of the carboxyl group-containing resin is suitably in the range of 10 to 60 mass%, preferably 20 to 50 mass%, in the photocurable resin composition. If the blending amount of the carboxyl group-containing resin is less than 10% by mass, the film strength may be lowered, which is not preferable. On the other hand, when it is more than 60% by mass, the viscosity of the photo-curable resin composition becomes high or the coatability to the carrier film is lowered.

When both the photosensitive carboxyl group-containing resin and the photosensitive group-containing carboxyl group-containing resin are used, the content ratio of the photosensitive carboxyl group-containing resin to the photosensitive group-containing resin is preferably in the range of (1: 9) (5: 5) to (7: 3), preferably from (2: 8) to (8: 2), more preferably from Within this range, it is possible to obtain a cured product of a resin composition and a printed wiring board having the same, which are excellent in both resolution and low warpage, while avoiding an increase in exposure dose.

The photosensitive resin containing a carboxyl group and the resin containing no photosensitive resin other than those described above may be used singly or in combination of a plurality of kinds. Of the carboxyl group-containing resins, resins having an aromatic ring are particularly preferred because of their high refractive index and excellent resolution, and those having a novolak structure are more preferable in terms of resolution, PCT resistance and crack resistance .

As the phenol resin, a compound having a phenolic hydroxyl group such as a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons thereof, or a compound having a phenolic hydroxyl group such as phenol, orthocresol, , Methacresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- A phenol resin having various skeletons synthesized by using norbornene, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, and fluoroglucinol may be used.

Examples thereof include phenol novolac resins, alkylphenol novolak resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, Xylok type phenol resins, terpene modified phenol resins, polyvinyl phenols, bisphenol F, bisphenol S type phenol resins , Poly-p-hydroxystyrene, condensates of naphthol and aldehydes, condensation products of dihydroxynaphthalene and aldehydes, and the like can be used.

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

Phenolite TD-2090, phenolite TD-2131 (manufactured by Dainippon Printing Co.), Bethmol CZ-256-A (manufactured by DIC), and Scholon BRG-555 CRO-70, C-90, S-1P, S-2P (manufactured by Maruzen Kogyo Co., Ltd.) of polyvinylphenol, and the like . These phenol resins may be used alone or in combination of two or more.

In the present invention, any one of a carboxyl group-containing resin and a phenol resin or a mixture thereof may be used as the alkali-soluble resin.

In the case of using a material not containing an ethylenic unsaturated group as the alkali-soluble resin (component A) in the photocurable resin composition of the present invention, it is preferable to use one having at least one ethylenic unsaturated group, It is necessary to use a compound, that is, a photopolymerizable monomer. The photopolymerizable monomer is photo-cured by irradiation with active energy rays to promote dissolution of the alkali-soluble resin in an aqueous alkali solution. In addition, even when a carboxyl group-containing resin is used, a photopolymerizable monomer can be used in combination for the purpose of further promoting photo-curing.

In either case, one kind or plural kinds of the following photopolymerizable monomers can be used.

[Component (B): photopolymerization initiator]

In order to form the resin composition of the present invention with a photocurable resin composition, a photopolymerization initiator is blended. The photopolymerization initiator is preferably at least one photopolymerization initiator selected from the group consisting of an oxime ester-based photopolymerization initiator having an oxime ester group, an? -Aminoacetophenone-based photopolymerization initiator, and an acylphosphine oxide-based photopolymerization initiator .

As the oxime ester-based photopolymerization initiator, commercially available products include CGI-325, Irgacure OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, Adeka Ariz NCI-831, etc., . Further, a photopolymerization initiator having two oxime ester groups in the molecule can be preferably used. Specifically, oxime ester compounds having a carbazole structure represented by the following general formula can be given.

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

In particular, it is preferable that X and Y are each a methyl group or an ethyl group, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene.

The blending amount of the oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (solid content). When the amount is less than 0.01 part by mass, the photocurability of the resin composition is insufficient, resulting in detachment of the coating film and deterioration of coating film properties such as chemical resistance. On the other hand, if it exceeds 5 parts by mass, the light absorption at the surface of the solder resist coating film becomes severe, and the deep portion curability tends to be lowered. More preferably 0.5 to 3 parts by mass.

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

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

The blending amount of the? -amino acetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (solid content). If the amount is less than 0.1 part by mass, the resin composition may have insufficient photocurability, resulting in peeling of the coating film and deterioration of coating film properties such as chemical resistance. On the other hand, if it exceeds 30 parts by mass, the effect of reducing the outgas is not obtained, and the light absorption at the surface of the solder resist coating film becomes severe, so that the deep portion curability tends to decrease. More preferably 0.5 to 15 parts by mass.

The resin composition of the present invention preferably uses an oxime ester-based photopolymerization initiator. By using the oxime ester-based photopolymerization initiator, sufficient sensitivity can be obtained even in a small amount, and since the volatilization of the photopolymerization initiator during thermal curing and post-heat treatment at the time of mounting is small, shrinkage of the cured coating film is suppressed It is possible to greatly reduce warpage.

It is also preferable to use an acylphosphine oxide-based photopolymerization initiator. By using acylphosphine oxide, phosphorus concentration in the cured coating film can be effectively increased by improving the deep curing property during the photoreaction and by inserting the initiator-containing phosphorus-containing compound component cleaved by light irradiation into the cured product network , Thereby further improving the flame retardancy.

Either the oxime ester-based photopolymerization initiator or the acylphosphine oxide-based photopolymerization initiator can be effectively used in the resin composition of the present invention. However, the above-mentioned line shape and opening balance of the resist, It is more preferable to use a combination of an oxime ester-based photopolymerization initiator and an acylphosphine oxide-based photopolymerization initiator in terms of low warping property, bending property and flame retardancy.

As the photo polymerization initiator, Irgacure 389 and Irgacure 784 manufactured by BASF Japan Co., Ltd. can also be preferably used.

In addition to the above-described photopolymerization initiator, in the present invention, a photoinitiator or sensitizer may be used.

[Photopolymerization initiation assistant and sensitizer]

Examples of the photoinitiator and sensitizer that can be preferably used in the resin composition of the present invention include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, And xanthone compounds.

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

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

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

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

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

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

Specific examples of the tertiary amine compound include an ethanolamine compound and a compound having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nissei, manufactured by Nippon Soda Co., Ltd.) (Diethylamino) -4-methyl-2H-1-benzo [epsilon]) such as 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Pyran-2-one (7- (diethylamino) -4-methylcoumarin), ethyl 4-dimethylaminobenzoate (Kayacure EPA manufactured by Nippon Kayaku Co., Dimethyl aminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Biosynthesis Inc.), p-dimethylaminobenzoic acid isoamyl (n-butoxyethyl) aminobenzoate (Quantacure DMB manufactured by International Biosynthesis Inc.) Ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 2-ethyl 4-dimethylaminobenzoate Chamber (Van Dyke (Van Dyk) solrol (Esolol) to the product of 507), 4,4'-diethylamino-benzophenone (Hodogaya Chemical Co., Ltd. Preparation EAB), and the like.

The tertiary amine compound is preferably a compound having a dialkylaminobenzene structure. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 450 nm, Is particularly preferable.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because it has low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet ray region, a colored solder resist film reflecting the color of the colored pigment itself as well as a colorless transparent photosensitive composition, And the like. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in that it exhibits an excellent effect of increasing or decreasing the laser light having a wavelength of 400 to 410 nm.

The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass (solid content) of the carboxyl group-containing resin.

When the compounding amount of the tertiary amine compound is less than 0.1 part by mass, there is a tendency that sufficient increase or decrease effect can not be obtained. On the other hand, when the amount exceeds 20 parts by mass, the light absorption at the surface of the dried solder resist coating film by the tertiary amine compound becomes severe, and the deep curing property tends to be lowered. More preferably 0.1 to 10 parts by mass.

Among the above-described photoinitiator and sensitizer, thioxanthone compounds and tertiary amine compounds are preferable. In particular, it is preferable that the thioxanthone compound is contained in view of the deep portion curing property of the resin composition. Among them, a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone is preferable Do.

The compounding amount of such a thioxanthone compound is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (solid content). If the compounding amount of the thioxanthone compound exceeds 20 parts by mass, the thick film curability may deteriorate and the cost of the product may increase. More preferably 10 parts by mass or less.

These photoinitiator and sensitizer may be used singly or as a mixture of two or more.

The total amount of the photopolymerization initiator, photoinitiator and sensitizer described above is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (solid content) in the alkali-developable photosensitive resin composition for a printed wiring board. If the amount exceeds 35 parts by mass, the curing property of the resin composition tends to be lowered due to the light absorption.

Further, since the above-mentioned photopolymerization initiator, photoinitiator and sensitizer absorb specific wavelengths, the sensitivity may be lowered depending on the case, and may function as an ultraviolet absorber. However, they are not used solely for the purpose of improving the sensitivity of the composition. Light of a specific wavelength is absorbed as needed to increase the photoreactivity of the surface to change the line shape and opening of the resist to vertical, tapered, and reverse tapered shapes, and improve the accuracy of line width and opening diameter .

[Component C: spherical silica filler having an average particle diameter of 300 nm or less]

In the resin composition of the present invention, a spherical silica filler having an average particle diameter of 300 nm or less (hereinafter also referred to as spherical nano silica) is used. Preferably 200 nm or less, and the lower limit is preferably 3 nm or more. The average particle diameter is measured by laser diffraction.

The spherical nanosilica used in the present invention is preferably a surface treated with a silane coupling agent. This can prevent precipitation or agglomeration after being dispersed in the liquid, and as a result, the storage stability is excellent. In addition, even when the composition is mixed, it can be stably introduced without aggregation. In addition, the wettability of the resin and filler of the resulting cured product can be improved.

Examples of organic groups contained in the silane coupling agent include vinyl groups, epoxy groups, styryl groups, methacryloxy groups, acryloxy groups, amino groups, ureido groups, chloropropyl groups, mercapto groups, polysulfide groups, isocyanates And the like.

Examples of commercially available products of the silane coupling agent include KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM- 503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM- KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846 and KBE-9007 (both trade names; manufactured by Shinsei Silicone Co., Ltd.). These may be used singly or in combination of two or more.

The spherical nano-silica of the present invention may be used singly or in combination of two or more kinds, and may be used in combination with other fillers as described later.

In the present invention, by using spherical nanosilica, the resolution of the resin composition can be remarkably improved.

The spherical nanosilica component in the photocurable resin composition can be a starting point for scattering light, and its light scattering has a great influence on the resolution. The light scattering phenomenon can be assumed to depend on the particle size of the nano silica particles from the theory of Rayleigh scattering and Mie scattering. This is because, as the size parameter of the scatterer becomes larger in the non-scattering formula, the scattering intensity of the light becomes stronger. Also, if the magnitude parameter is sufficiently small with respect to the wavelength of light, the scattering intensity becomes small.

Therefore, light scattering can be suppressed by reducing the size of the spherical nanosilica than the wavelength of light used for exposure, and a photo-curable resin composition excellent in resolution can be obtained in the present invention.

Further, the spherical nanosilica of the present invention has good dispersibility in the resin and is spherical, so that occurrence of cracks in the cured coating is satisfactorily reduced. In addition, it is possible to reduce the occurrence of warpage even in high-temperature electrolysis and to improve the bending resistance.

Examples of other fillers that can be used in combination with spherical nano-silica are spherical silica fillers having an average particle size exceeding 300 nm, or other inorganic or organic fillers, such as alumina, barium sulfate, talc, and neuburger silica particles. As the filler capable of imparting flame retardancy, aluminum hydroxide, magnesium hydroxide, and boehmite can also be used.

In addition, the spherical nanosilica used in the present invention may be spherical, and is not limited to spherical silica. As the preferable component (C), for example, the degree of sphericity as measured below is 0.8 or more.

The sphericity is measured as follows. A photograph is taken with an SEM and is calculated as the value calculated from the area and the circumferential length of the observed particle by (squareness) = {4 pi x (area) / (circumferential length) ² }. Specifically, an average value measured for 100 particles is adopted by using an image processing apparatus.

The method for producing spherical silica particles is not particularly limited, and a method known to those skilled in the art can be applied. For example, a silicon powder can be produced by burning by VMC (Vaporized Metal Combustion) method. The VMC method is a method in which a chemical salt is formed by a burner in an atmosphere containing oxygen and a metal powder constituting a part of the objective oxide particles is introduced into the chemical salt in such an amount as to form a dust cloud Thereby causing the detonation to obtain oxide particles.

The amount of the spherical nano-silica in the resin composition of the present invention is preferably 60% by mass or more, more preferably 70% by mass or more, particularly preferably 70% by mass or more, in the total composition (in terms of solid content) And not more than 85% by mass. When the amount of the spherical nano-silica is less than 60% by mass, the viscosity of the curable resin composition is lowered, and the printed property is lowered and the curability of the cured product is lowered.

A filler of a different kind may be added so that the spherical silica filler (component C) of the present invention occupies 50% by mass or more, preferably 80% by mass or more, based on the total amount of the filler.

Further, the blending amount of the nano silica can be clearly determined by measuring the amount of the residue after combustion. More specifically, the conditions for the combustion can be measured by TG-DTA (manufactured by Hitachi High-Technologies Science Co., Ltd.) set at 800 to 1000 ° C.

In addition, a compound having at least one ethylenic unsaturated group or NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, Hanse-Chemie Co., Ltd. in which nanosilica is dispersed in a polyfunctional epoxy resin, XP 0716, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all product class names) and NANOPOX (product name) manufactured by Hans- Can also be used. In this case as well, the total amount of the nano-silica to be blended and the total amount of the blend containing the blended filler is the same as described above.

[Photopolymerizable monomer]

The photocurable resin composition of the present invention may contain a photoreactive monomer for publicly known generations. The photopolymerizable monomer is a compound having at least one ethylenic unsaturated group in the molecule. The photoreactive monomer is to assist the photocuring of the carboxyl group-containing resin by irradiation with active energy rays.

As the compound used as the photopolymerizable monomer, for example, known compounds such as polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) Methacrylate, and the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates such as water; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and acrylates and melamine acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene or a polyester polyol, or a urethane acrylate through a diisocyanate, and And at least one of the respective methacrylates corresponding to the acrylate.

Among them, the use of a photopolymerizable monomer having an aromatic ring is preferable from the viewpoint of reduction of warpage.

In addition, epoxy acrylate resins obtained by reacting polyfunctional epoxy resins such as cresol novolak type epoxy resins with acrylic acid, or epoxy acrylate resins obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate with isophorone An epoxy urethane acrylate compound in which a half urethane compound of a diisocyanate such as a diisocyanate is further reacted may be used as a photoreactive monomer. Such an epoxy acrylate resin can improve the photocurability without lowering the composition of the touch and dry.

The blending amount of the photopolymerizable monomer is 5 to 100 parts by mass, more preferably 5 to 70 parts by mass, based on 100 parts by mass (solid content) of the photosensitive resin containing a carboxyl group and the resin having no photosensitive resin.

If the blending amount is less than 5 parts by mass, the photocurability is lowered, and pattern formation becomes difficult due to the alkali development after irradiation with active energy rays, which is not preferable. On the other hand, if it exceeds 100 parts by mass, the solubility in an aqueous alkali solution is lowered and the coating film may be decomposed, which is not preferable.

[Thermosetting component]

The photo-curable resin composition of the present invention can be thermally cured in addition to photo-curing.

By further thermally curing the resin composition after photo-curing, properties such as heat resistance and insulation reliability of the cured product can be improved.

Examples of the thermosetting component include known compounds such as isocyanate compounds, block isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds and episulfide resins Of thermosetting resin can be used.

In the present invention, an epoxy resin (D) is particularly preferably used.

As the epoxy resin, a known multi-functional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be in liquid form, or may be solid or semi-solid.

Examples of the epoxy resin include epoxy resins such as jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, epiclon 840 manufactured by DIC, epiclon 850, epiclon 1050, epiclon 2055, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Sumi-epoxy ESA-011 and ESA-014 manufactured by Sumitomo Chemical Co., Bisphenol A type epoxy resins such as ELA-115, ELA-128, AER330, AER331, AER661, AER664 (all trade names) manufactured by Asahi Kasei Corporation; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 manufactured by DIC Corporation, Epiclon 165, Epototo YDB-400, YDB-500 manufactured by Dotogasei Co., Ltd., DER542 manufactured by Dow Chemical Company, manufactured by Sumitomo Chemical Co., Brominated epoxy resins such as Sumi-epoxy ESB-400, ESB-700, AER711 and AER714 manufactured by Asahi Kasei Corporation; JER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431 and DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 and NC-3000 manufactured by Nippon Kayaku Co., Ltd., SUMI EPOXY ESCN-195X manufactured by Sumitomo Chemical Co., AERECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, and YDCN manufactured by Shin-Nittsu Chemical Co., -700-10, YDCN-704 YDCN-704 A, Epiclon N-680, N-690 and N-695 (all trade names) manufactured by DIC Corporation; Bisphenol F type epoxy resins such as Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Chemical Corporation, Epitoto YDF-170, YDF-175 and YDF-2004 manufactured by Tokto Kasei Co., Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokuga Seisakusho; A glycidylamine type epoxy resin such as jER604 manufactured by Mitsubishi Kagaku Co., Ltd., Epitoto YH-434 manufactured by Tokuga Seisakusho Co., Ltd. and SUMIEPOX ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names) Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 (all trade names) manufactured by Daicel Chemical Industries, Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501 and EPPN-502 manufactured by Dow Chemical Co., Ltd. (all trade names), trihydroxyphenylmethane type epoxy resin; Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., EPX-30 manufactured by Adeka Co., and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak type epoxy resins such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resins such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; A heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); Diglycidyl phthalate resins such as Blumer DGT manufactured by Nippon Oil Polymer Co., Ltd.; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Toko Chemical Co., Ltd.; Epoxy resin containing naphthalene group such as ESN-190, ESN-360 manufactured by Shinnitetsu Chemical Industries, HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nippon Yushi Co., Ltd.; A copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; And CTBN-modified epoxy resins (for example, YR-102 and YR-450 manufactured by Tokuga Seisakusho Co., Ltd.). However, the present invention is not limited thereto.

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

In the present invention, among the epoxy resins, an epoxy resin (component D-1) having a naphthalene structure is preferably used. By using an epoxy resin having a naphthalene structure, the low warpage property and the flame retardancy of the cured product are improved.

Specific examples of commercially available materials include ESN-190, ESN-360 (manufactured by Shinnitetsu Chemical Industries) and HP-4032, EXA-4750 and EXA-4700 (manufactured by DIC).

These curable resins may be used alone or in combination of two or more. By using an epoxy resin having a naphthalene structure, flexibility of the cured coating film can be improved and the coefficient of linear expansion can be lowered.

The blending amount of the thermosetting component is 5 parts by mass to 50 parts by mass, preferably 10 to 30 parts by mass, based on 100 parts by mass (solids content) of the photosensitive resin containing a carboxyl group and the resin having no photosensitive resin.

The photocurable resin composition of the present invention can be constituted by using an additive such as a colorant, a predetermined copolymer, a binder polymer, an elastomer, an adhesion promoter, an antioxidant and an ultraviolet absorber, and an organic solvent. These components will be described below.

[coloring agent]

In the curable resin composition of the present invention, a colorant may be added.

As the colorant, publicly known colorants such as red, blue, green, and yellow can be used, and any of pigments, dyes, and pigments may be used. Specifically, a color index (issued by the Society of Dyers and Colourists, published by CI.) Is attached as follows. However, it is preferable that the colorant is a halogen-free colorant from the viewpoint of environmental load reduction and human influence.

Red colorant:

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

Monoazo system: Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 112, 114, 146, 147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Disazo system: Pigment Red 37, 38, 41.

48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68.

Benzimidazolone pigments: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 174, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, .

Diketopyrrolopyrrole-based pigments: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone pigments: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Examples of the blue colorant include a phthalocyanine type and an anthraquinone type, and a pigment type is a compound classified as a pigment. Specific examples thereof include Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60.

Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, 70 may be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Green colorant:

Examples of the green colorant include phthalocyanine type, anthraquinone type and perylene type. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28 and the like can be used . In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

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

Anthraquinone series: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone pigments: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone pigments: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo system: Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 61, 62, 62: 1, 65, 73, 74, 75, 97, 100, 104, 105, 111 , 116, 167, 168, 169, 182, 183.

Disazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

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

Specific examples include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 3, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, and the like.

The mixing ratio of the colorant is not particularly limited, but is preferably 0 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass (solids content) of the total amount of the photosensitive carboxyl group-containing resin and the non- Ratio.

[Binder polymer]

For the purpose of improving the flexibility and tack dryness of the resulting cured product, a binder polymer known in the art can be used in the resin composition of the present invention.

As the binder polymer, a cellulose-based, polyester-based, or phenoxy resin-based polymer is preferably used.

Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Kodak Company,

As the polyester polymer, Byron series manufactured by Toyo Bosa Co.,

As the phenoxy resin polymer, bisphenol A, bisphenol F, and phenoxy resins of hydrogenated compounds thereof are preferable.

The amount of the binder polymer to be added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, particularly preferably 5 to 30 parts by mass, based on 100 parts by mass of the total amount of the photosensitive resin containing a carboxyl group and the resin having no photosensitivity. 30 parts by mass. When the blending amount of the binder polymer is more than 50 parts by mass, the alkali developability of the curable resin composition is lowered, and the development available time is shortened, which is not preferable.

[Y-X-Y type block copolymer]

The photo-curable resin composition of the present invention can be used in combination with a block copolymer. The block copolymer generally refers to a copolymer of a molecular structure having two or more kinds of polymer units having different properties, which are covalently linked to form a long chain.

When the YXY type block copolymer and the spherical silica filler having an average particle diameter of 300 nm or less are used in combination, cracking is suppressed in the cured product obtained by the photocurable resin composition of the present invention, and the resolution is further improved, do.

The block copolymer used in the present invention has the following formulas (I),

Y-X-Y (I)

Y is a polymer unit having a glass transition point (Tg) of 0 占 폚 or higher, preferably 50 占 폚 or higher and X is a polymer unit having a glass transition point (Tg) lower than 0 占 폚, preferably lower than or equal to -20 占 폚 being)

, And more preferably a solid at 20 占 폚 or higher and 30 占 폚 or lower.

As described above, it is considered that a specific structure in a matrix tends to be expressed by making a block copolymer at both ends commercially available in a matrix and a central block in a matrix for an emergency.

As the polymer unit Y, polymethyl methacrylate (PMMA), polystyrene (PS) and the like are preferable, and as the polymer unit X, poly n-butyl acrylate (PBA) and polybutadiene (PB) When a hydrophilic unit having excellent compatibility with the above-mentioned carboxyl group-containing resin typified by a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy-containing unit, an N-substituted acrylamide unit, It is possible to further improve the compatibility.

Examples of the method for producing the block copolymer include the methods described in Japanese Patent Application No. 2005-515281 and Japanese Patent Application No. 2007-516326.

Specifically, in the formula (I)

Y is a polystyrene, polyglycidyl methacrylate, or N-substituted polyacrylamide, polymethyl (meth) acrylate or a carboxylic acid modified product or a hydrophilic modified product thereof, and X is a poly n- Or polybutadiene.

Commercially available products of the Y-X-Y block copolymer include acrylic triblock copolymers produced by living polymerization produced by Arkema. Specific examples include MAM type (for example, M51, M52, M53, M22) represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate, a carboxylic acid-modified MAM A type (For example, SM4032XM10), and MAM N type (for example, 52N and 22N) treated with a hydrophilic group.

Further, it is preferable that the mass average molecular weight (Mw) of the block copolymer is 20000 or more and 400,000 or less and in the range of 30,000 to 300,000. It is preferable that the molecular weight distribution (Mw / Mn) is 3 or less.

If the mass average molecular weight is less than 20,000, the effect of toughness and flexibility can not be obtained, and the tack property is also lowered. On the other hand, when the mass average molecular weight exceeds 400,000, the viscosity of the curable resin composition becomes high, and the printability, developability, and the like are remarkably deteriorated.

The blending amount of the block copolymer is preferably from 1 to 50 parts by mass, more preferably from 5 to 35 parts by mass, based on 100 parts by mass (solid content) of the carboxyl group-containing resin (A).

When the amount is less than 1 part by mass, the effect can not be expected. When the amount is more than 50 parts by mass, the photocurable resin composition is not preferable because development and coatability are likely to deteriorate.

[Elastomer]

The resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the obtained cured product and improving the fragility of the cured product.

Examples of the elastomer include a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer, and an olefin elastomer.

In addition, a resin obtained by modifying epoxy groups of some or all of epoxy resins having various skeletons with both terminal carboxylic acid modified butadiene-acrylonitrile rubbers can also be used.

Further, an epoxy-containing polybutadiene elastomer, an acrylic-containing polybutadiene elastomer, a hydroxyl group-containing polybutadiene elastomer, and a hydroxyl group-containing isoprene elastomer may be used.

The elastomer may be used singly or as a mixture of two or more kinds.

[Adhesion promoter]

To the resin composition of the present invention, an adhesion promoter may be used to improve interlayer adhesion or adhesion between the photosensitive resin layer and the substrate.

Examples of the adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3- 1-phenyl-triazole-2-thione, 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto- Benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.

[Antioxidant]

Most of the polymer materials, once oxidized, are oxidatively deteriorated successively, resulting in degradation of the function of the polymer material. The resin composition of the present invention contains (1) a radical supplements for nullifying the generated radicals, and (2) an antioxidant such as a peroxide decomposer for decomposing the generated peroxide into a harmless substance to prevent generation of new radicals Can be added.

Specific examples of the radical supplements include hydroquinone, 4-tert-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2,6-di- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4 Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'- Phenol-based compounds such as S-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as methoquinone and benzoquinone, bis (2,2,6,6-tetramethyl- - piperidyl) sebacate, phenothiazine, and the like.

Radical supplements may be commercially available, for example, Adeka Stab AO-30, Adeka Staff AO-330, Adeka Staff AO-20, Adeka Staff LA-77, Adeka Staff LA-57, (Manufactured by Asahi Kasei Kogyo Co., Ltd.), IRGANOX 1010, Irganox 1035, Irganox 1076, Irgacox LA-67, Adeka Staff LA- TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (trade names, manufactured by BASF Japan), and the like.

Specific examples of the antioxidant functioning as a peroxide releasing agent include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetra lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-t- And sulfur compounds such as octyl propionate.

The release of the peroxide may be commercially available, and examples thereof include Adekastab TPP (trade name, manufactured by Asahi Kasei), Mark AO-412S (trade name, manufactured by Adeka Agusugaku Co., Ltd.), Sumilai TPS Trade name, manufactured by Kagaku Kogyo Co., Ltd.).

The antioxidant may be used alone or in combination of two or more.

[UV absorber]

Since the polymer material absorbs light and causes decomposition or deterioration thereof, the resin composition of the present invention can use an ultraviolet absorber in addition to the antioxidant in order to take measures against stabilization against ultraviolet rays.

Examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives.

Specific examples of the benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone, 2-hydroxy- Dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone and the like,

Specific examples of the benzoate derivative include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di- -Hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate,

Specific examples of benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di- Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, and the like of,

Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

Examples of the ultraviolet absorber include commercially available ultraviolet absorbers such as Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, TINUVIN 405, TINUVIN 460 and TINUVIN 479 (all trade names, manufactured by BASF Japan).

The ultraviolet absorber may be used alone or in combination of two or more. By using in combination with an antioxidant, the molded article obtained from the curable resin composition of the present invention can be stabilized.

[Other additives]

In the resin composition of the present invention, additives such as a thermal polymerization inhibitor, a thickening agent, a defoaming agent, a leveling agent, a silane coupling agent, and a rust inhibitor may be further used if necessary.

Among them, examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine,

Examples of the thickening agent include fine silica, organic bentonite, montmorillonite,

As the at least one of the antifoaming agent and the leveling agent, silicon, fluorine,

As the silane coupling agent, an imidazole-based, thiazole-based, triazole-based or the like can be used. Additives can be formulated.

The thermal polymerization inhibitor can be used to prevent unwanted thermal polymerization or aging polymerization of the resin composition.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butyl catechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy- Phenol, cuprous chloride, phenothiazine, chloranil, naphthylamine,? -Naphthol, 2,6-di-t-butyl-4-cresol, 2,2'- t-butyl phenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, reagents with organic chelating agents with copper, methyl salicylate, phenothiazine, nitroso compounds, And the like.

[Organic solvents]

In the present invention, an organic solvent may be used. The organic solvent may be selected from the group consisting of the synthesis of a carboxyl group-containing resin, the components A to C, the case where components D, E and F and the necessary additives are mixed and the viscosity of the resulting photosensitive resin composition is adjusted on a substrate or a carrier film Is used.

Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like.

More specifically, ketones such as methyl ethyl ketone and cyclohexanone,

Aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene,

Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether Glycol ethers such as < RTI ID =

Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate,

Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol,

Aliphatic hydrocarbons such as octane and decane,

Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.

These organic solvents may be used singly or as a mixture of two or more kinds.

The curable resin composition of the present invention may be in the form of a dry film having a carrier film (support) and a layer containing a curable resin composition formed on the carrier film.

In the case of the dry film formation, the curable resin composition of the present invention is diluted with an organic solvent and adjusted to an appropriate viscosity, and the resulting mixture is kneaded by a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Coater or the like to a uniform thickness on the carrier film and dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

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

It is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing the adhesion of dust to the surface of the film after the resin composition of the present invention is formed on the carrier film.

As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. The adhesion force between the film and the cover film is made smaller than the adhesion force between the film and the carrier film in consideration of peeling of the cover film.

The resin composition of the present invention can be prepared by a method such as dip coating method, flow coating method, roll coating method, bar coater method, screen printing method, curtain coating method, etc. , And the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 DEG C, whereby a tack-free coating film can be formed. In the case of a dry film obtained by applying the composition onto a carrier film and drying the film, the film is bonded to the base material by a laminator or the like so as to be in contact with the base material, and then the carrier film is peeled off, Can be formed.

As the substrate, in addition to a circuit board or a flexible printed circuit board which has been formed on a circuit formed in advance, a substrate such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, (FR-4 and the like), other polyimide films, PET films, glass substrates, ceramic substrates, and wafer plates using a material such as a copper clad laminate for a high frequency circuit using phenylene ether, cyanate ester resin, And the like.

The volatile drying performed after applying the photocurable resin composition of the present invention can be carried out by a hot-air circulating drying furnace, a hot plate, a convection oven or the like (a furnace equipped with a heat source of air heating by steam, A method of countercurrent contact with the support and a method of spraying the support from the nozzle).

In the present invention, the photo-curable resin composition or the solvent of the dry film is volatilized and dried, and the resulting coating film is subjected to exposure (irradiation with active energy rays) to cure the exposed portion (the portion irradiated with the active energy rays) .

For example, the photocurable resin composition after drying or the dry film can be exposed to an active energy ray by a contact or noncontact method through a photomask having a pattern formed thereon. In addition, the exposed portion can be photo-cured by directly pattern-exposing the photocurable resin composition or the dry film by a laser direct exposure machine.

In any of the above methods, the unexposed portion can be developed with a dilute alkali aqueous solution (for example, a 0.3 to 3 wt% aqueous solution of sodium carbonate) to form a resist pattern.

As an exposure apparatus used for irradiation with active energy rays, an apparatus for irradiating ultraviolet rays in a range of 350 to 450 nm may be used as long as it is equipped with a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, or a mercury short arc lamp.

It is also possible to use a direct drawing apparatus (for example, a laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer). As a laser light source of a direct shot, any of a gas laser and a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used.

Light exposure for image formation is different depending on the thickness, in general, it can be set within 20 to 800mJ / cm ^2, preferably in the range of 20 to a range of 600mJ / cm ^2.

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

When the flame-retardant curable resin composition of the present invention contains a thermosetting component, the carboxyl group of the carboxyl-containing resin reacts with the thermosetting component by heating to a temperature of, for example, about 140 to 180 ° C, , A cured coating film excellent in various properties such as chemical resistance, hygroscopicity, adhesion, electrical characteristics and the like can be formed.

The present invention will be described in further detail with reference to the following examples. The present invention is not limited to the following examples at all. In the examples, " part " and "% " of the amount of material used are based on mass unless otherwise specified.

The photocurable resin composition of the present invention is preferable as a permanent film of a printed wiring board, and is particularly preferable as a solder resist or an interlayer insulating material.

[Example]

[Examples 1 to 9 and Comparative Examples 1 to 4]

Each material was compounded with the composition shown in Table 1 described later, preliminarily mixed with an agitator, and then kneaded by a three-roll mill to prepare a thermosetting resin composition.

Further, a photosensitive resin solution containing a carboxyl group, a resin solution containing a carboxyl group having no photosensitivity, and silica (on a slurry) were prepared by the following procedure.

[Synthesis of Photosensitive Carboxyl Group-Containing Resin Solution A-2]

119.4 g of a novolak type cresol resin (manufactured by Showa Denko K.K., CRG951, OH equivalent: 119.4), a hydroxylamine, a nitrogen introducing device and an alkylene oxide introducing device and an autoclave equipped with a stirrer, 1.19 g of potassium and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating.

Then, 63.8 g of propylene oxide was gradually added dropwise from the alkylene oxide introducing device and reacted at 125 to 132 캜 and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature. To the reaction solution, 1.56 g of 89% phosphoric acid was added and mixed to neutralize the potassium hydroxide to obtain a propylene oxide of a novolak type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / To obtain a reaction solution. This means that an average of 1.08 moles of alkylene oxide per 1 equivalent of the phenolic hydroxyl group was obtained.

293.0 g of the alkylene oxide reaction solution of the obtained novolak type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methylhydroquinone and 252.9 g of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air- Was blown at a rate of 10 ml / min and reacted at 110 DEG C for 12 hours while stirring. The water produced by the reaction was 12.6 g of water as an azeotropic mixture with toluene.

Thereafter, the obtained reaction solution was cooled to room temperature, neutralized with 35.35 g of a 15% aqueous solution of sodium hydroxide, and then washed with water. The toluene was distilled off by replacing the toluene with 118.1 g of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolak type acrylate resin solution. Further, 332.5 g of the obtained novolak type acrylate resin solution and 1.22 g of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer and an air inlet tube, and air was blown at a rate of 10 ml / 60.8 g of hydrophthalic anhydride was slowly added and the reaction was carried out at 95 to 101 ° C for 6 hours.

Thus, a resin solution of a carboxyl group-containing photosensitive resin having an acid value of 88 mg KOH / g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as a varnish A-2.

[Synthesis of carboxyl-containing resin solution A-1 having no photosensitivity]

119.4 g of a novolak type cresol resin (manufactured by Showa Denko K.K., CRG951, OH equivalent: 119.4), a hydroxylamine, a nitrogen introducing device and an alkylene oxide introducing device and an autoclave equipped with a stirrer, 1.19 g of potassium and 119.4 g of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating.

Subsequently, 63.8 g of propylene oxide was gradually added dropwise, and the mixture was reacted at 125 to 132 캜 and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature. To the reaction solution, 1.56 g of 89% phosphoric acid was added and mixed to neutralize the potassium hydroxide to obtain a propylene oxide of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g / To obtain a reaction solution. This means that an average of 1.08 moles of alkylene oxide per 1 equivalent of the phenolic hydroxyl group was obtained.

Then, 293 g of the above product and 1.22 g of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air inlet tube, and 152 g of tetrahydrophthalic anhydride (molecular weight 152) was blown into the reactor while blowing air at a rate of 10 ml / The reaction was allowed to proceed at 95 to 101 ° C for 6 hours.

Thus, a resin solution of a carboxyl group-containing resin having an acid value of 100 mgKOH (56) / g of solid matter and 75% of nonvolatile matter was obtained. Hereinafter, this is referred to as a varnish A-1.

[Preparation of spherical silica slurry]

, 495 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5 g of a vinylsilane coupling agent as a silane coupling agent were mixed and stirred, and dispersion treatment was carried out using zirconia beads having a diameter of 0.5 mu m with a bead mill . This was repeated three times and filtered with a 3 탆 filter to prepare silica slurries having an average particle diameter of 150 nm, 200 nm, 300 nm, 450 nm and 770 nm.

* 1: 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide (Lucirin TPO: BASF Japan)

* 2: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1,1- (O- acetyloxime) (Irgacure OXE 02: BASF Japan)

* 3: spherical silica slurry manufactured by Adma Tech Co., Ltd.

* 4: C.I. Pigment Blue 15: 3

* 5: C.I. Pigment Yellow 147

* 6: 2-mercaptobenzothiazole

* 7: Diethylene glycol monoethyl ether acetate

* 8: Naphthalene type epoxy resin (ESN-355: manufactured by Shin-Nittsu Chemical Co., Ltd.)

* 9: Bisphenol-type epoxy resin (YSLV-80XY: manufactured by Toko Chemical Co., Ltd.)

* 10: Dipentaerythritol pentaacrylate

* 11: Tricyclodecane dimethanol diacrylate

* 12: Fuselex WX (manufactured by Tatsumori)

Using the photocurable resin composition (varnish) prepared in Examples 1 to 9 and Comparative Examples 1 to 4, a sample for evaluation was produced by the following procedure.

<1-1. Preparation of sample for evaluation of optimum exposure dose >

The circuit pattern substrate having a copper thickness of 18 mu m was subjected to surface roughening treatment using a copper surface roughening agent (Mck etch bond (registered trademark) CZ-8100, manufactured by Mack Co., Ltd.), followed by washing with water.

Then, the photocurable resin compositions of Example 1-9 and Comparative Example 1-4 were coated on the entire surface of the substrate by a screen printing method and dried in a hot air circulation type drying furnace at 80 캜 for 30 minutes. The thickness of the dried resin composition was 20 占 퐉. This was used as a sample for measuring the optimum exposure dose described below.

<1-2. Optimum exposure dose>

(Kodak No. 2) was placed between the exposure apparatus and the evaluation sample, exposure was performed on each evaluation sample. The step tablet is a film having a concentration gradient, and is exposed between the sample and the exposure apparatus, whereby exposure is performed with a single oblique exposure in which the exposure amount increases by 21 steps per sample.

The evaluation sample after exposure was developed at 30 캜 for 90 seconds using 0.2% by weight aqueous sodium carbonate solution. The amount of light of the exposure apparatus was adjusted so that the resin from the side of the step tablet having a high film density (light transmittance was small) to the level corresponding to the eighth step of division was uncured and removed by development. The amount of light used for curing the resin was evaluated according to the following criteria.

?: Exposure dose less than 300 mJ / cm ²

?: Exposure dose of 300 mJ / cm ² or more and less than 500 mJ / cm ²

X: An exposure dose of 500 mJ / cm ² or more

<2-1. Preparation of samples for evaluation of cold shock resistance &amp;

A solution obtained by appropriately diluting each of the photocurable resin compositions of Examples 1-9 and 1-4 with methyl ethyl ketone was applied to a PET carrier film (FB-50, manufactured by Toray Co., Ltd., 16 mu m) using an applicator And dried at 80 DEG C for 30 minutes. The film thickness of the dried dry film was 20 占 퐉.

The obtained dry film was bonded to a circuit pattern substrate having a copper thickness of 18 mu m using a vacuum laminator so that the curable resin layer was in contact with the substrate. The substrate was exposed to a solder resist pattern at the optimum exposure dose using the exposure apparatus equipped with a high-pressure mercury short arc lamp (? Blanking,? Blanking), and then the PET carrier film was peeled off.

And then developed with a 1 mass% sodium carbonate aqueous solution at 30 캜 for 60 seconds at a spray pressure of 0.2 MPa to obtain a solder resist pattern. This substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure dose of 1000 mJ / cm ² in a UV conveyer, and then cured by heating at 160 캜 for 60 minutes. The printed wiring board thus obtained was used as a sample for evaluation of cold-shock resistance.

<2-2. Evaluation of cold and heat shock resistance>

The sample for evaluation of cold / heat shock resistance was held at -55 占 폚 for 30 minutes, then heated to 125 占 폚, and held for 30 minutes by using a cold / impact tester (manufactured by ETAC Co., Ltd.). This test was carried out for one cycle, and the test was conducted for 500 cycles.

After the test, the cured product pattern after the treatment was visually observed to evaluate the occurrence of cracks. The criteria are as follows.

○: Less than 20% cracking occurrence rate

C: Cracking rate of 30% or more and less than 50%

×: Crack generation rate of 50% or more

<3-1. Preparation of Sample for Evaluation of Resolution >

A sample for evaluation of resolution was prepared in the same manner as in the production of the sample for evaluation of cold shock resistance and heat shock resistance. However, in this test, instead of blanking and blanking, pattern exposure was performed so as to form openings of 80 mu m in the dry film. This was used as a sample for the following resolution evaluation.

<3-2. Resolution evaluation>

An opening having an opening diameter of 80 mu m was observed with an SEM (scanning electron microscope) and evaluated according to the following criteria.

Good: Good shape in which Cu at the bottom of the opening is identified

X: Defect of opening shape in which Cu in the bottom of the opening is not confirmed

<4-1. Fabrication of Samples for Evaluation of Curvature>

The photocurable resin composition of Example 1-9 and Comparative Example 1-4 was applied to a 35 mu m thick copper foil. This was used as a sample for evaluation of warping below.

<4-2. Warpage evaluation>

The sample for evaluation of warpage was cured under the same conditions as in 2-1 to form a cured product. The cured product was cut into a square of 50 mm x 50 mm in the state of holding a copper foil, and the warpage of the quadrangle was measured to obtain an average value.

○: The warpage is less than 10 mm.

?: The warpage is 10 mm or more and less than 15 mm.

X: One having a warp of 15 mm or more.

<5-1. Preparation of sample for evaluation of HAST resistance >

A sample for evaluating HAST resistance was prepared in the same manner as the preparation of the sample for evaluation of cold shock resistance. For this test, the dry film was formed on a BT substrate on which a comb-shaped electrode (line / space = 15 micrometers / 15 micrometers) was formed instead of a circuit pattern substrate having a copper thickness of 18 μm and subjected to electrolytic gold plating. This was used as a sample for evaluation of HAST resistance.

<5-2. Evaluation of HAST resistance>

The sample for evaluation of HAST resistance was placed in a high-temperature, high-humidity bath under an atmosphere at 130 캜 and a humidity of 85%, charged at 5.5 V, and subjected to a HAST test in the bath for 168 hours.

The insulation resistance value in the bath at the elapsing time of 168 hours was measured to evaluate the HAST resistance. The criteria are as follows.

○: more than 10 ⁸ Ω

?: 10 ⁶ to 10 ⁸ ?

×: Less than 10 ⁶ Ω or short circuit

The resin compositions of Examples 1 to 15 and Comparative Examples 1 to 4 were subjected to a temperature condition of 800 to 1000 占 폚 using TG / DTA6200 manufactured by Hitachi High-Technologies Science Co., Ltd., and the amount of silica blended (amount of residue) was measured.

The test results are shown in Table 2 below.

Considering the results of the above tests, the photocurable resin composition of the present invention showed satisfactory results in terms of exposure dose, resolution, warpage, cold shock resistance and HAST resistance.

On the other hand, in the comparative examples, nano silica having a particle diameter of 300 nm or less was not used, or the cured product obtained had a balance of good characteristics as in the present invention, with less than 60% by mass based on the total amount of the photocurable resin composition It was not done.

The present invention is not limited to the configuration and the embodiment of the above-described embodiment, but various modifications are possible within the scope of the gist of the invention.

Claims (10)

(A) an alkali-soluble resin,
(B) a photopolymerization initiator, and
(C) a spherical silica filler having an average particle diameter of 300 nm or less
Wherein the photocurable resin composition is a photocurable resin composition,
Wherein the amount of the spherical silica filler (C) having an average particle size of 300 nm or less is 60% by mass or more based on the total amount of the photocurable resin composition. The photocurable resin composition according to claim 1, wherein the alkali-soluble resin (A) is a carboxyl group-containing resin having no photosensitive group (A-1). The photocurable resin composition according to claim 2, wherein the alkali-soluble resin further comprises a carboxyl group-containing resin having (A-2) a photosensitive group. The photocurable resin composition according to any one of claims 1 to 3, further comprising (D) an epoxy resin. The photocurable resin composition according to any one of claims 1 to 4, wherein the epoxy resin (D) is an epoxy resin having a (D-1) naphthalene structure. The photosensitive resin composition according to any one of claims 1 to 5, wherein the carboxyl group-containing resin having no photosensitive group (A-1) is a carboxyl group-containing resin obtained by reacting a polyphenol compound with an alkylene oxide-modified polyalcohol resin with a polybasic acid anhydride Wherein the resin is a resin. The photosensitive resin composition according to any one of claims 1 to 6, wherein the (A-2) carboxyl group-containing resin having a photosensitive group is obtained by reacting (meth) acrylic acid with a polyalcohol resin obtained by modifying an alkylene oxide- Is a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with an alkaline aqueous solution. A photocurable dry film obtained by applying and drying the photocurable resin composition according to any one of claims 1 to 7 on a carrier film. A cured product obtained by photo-curing a photo-curable resin composition according to any one of claims 1 to 7, or a photo-curable dry film obtained by applying and drying the photo-curable resin composition to a film. A photocurable resin composition according to any one of claims 1 to 7, or a photocurable dry film obtained by applying and drying the photocurable resin composition described above onto a substrate to provide a film of the photocurable resin composition Curing the coating film by irradiation of an active energy ray, and then thermally curing the coating film.