KR102167486B1 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

(D-1) 광반응성의 표면 처리가 된 무기 필러를 함유하는 경화성 수지 조성물이다.[Problem] To provide a curable resin composition suitable for use in printed wiring boards and the like and excellent in reliability and adhesion.
[Solution means] (A) a carboxyl group-containing resin, (B-1) a photopolymerization initiator, (C) an epoxy resin having the following structural formula,

(D-1) It is a curable resin composition containing an inorganic filler subjected to photoreactive surface treatment.

Description

Curable resin composition, dry film, cured product, and printed wiring board {CURABLE RESIN COMPOSITION, DRY FILM, CURED PRODUCT AND PRINTED WIRING BOARD}

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

Conventionally, as a material for forming a permanent film such as a solder resist, an interlayer insulating layer, and a coverlay of a printed wiring board, Patent Document 1 discloses a carboxyl group-containing polyurethane and a polyfunctional aliphatic glycidyl ether compound having a total chlorine content of less than 0.7% by mass. A thermosetting resin composition containing: is disclosed.

In recent years, with the rapid progress of semiconductor components, electronic devices tend to be light, thin, short, high-performance, and multifunctional. Following this trend, miniaturization and multi-pinization of semiconductor packages are being put into practical use.

Specifically, instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc., it is called BGA (ball grid array), CSP (chip scale package), etc. An IC package called is being used. In addition, in recent years, FC-BGA (flip chip, ball, grid, array) is also becoming more practical as a high-density IC package.

In a printed wiring board (also referred to as a package board) used for such an IC package, since the SRO (Solder Resist Opening) pitch is narrow and formed in close proximity to each other, there is a high possibility that a short circuit or crosstalk noise may occur between SROs. . Further, since the solder resist formed between the SROs becomes thin and thin, cracks tend to occur. Therefore, high reliability over a long period of time, specifically high insulation reliability, is required for a permanent film such as a solder resist used for a package substrate. In particular, it is expected that the demand for reliability will increase further with the higher density of the package substrate in the future.

Japanese Patent No. 51712113 Specification Japanese Patent Publication No. 2010-54912

However, with respect to this reliability, the thermosetting resin composition described in Patent Document 1 described above cannot be said to be sufficient in recent years.

In addition, in recent years, as the number of pins of ICs increases, the wiring distance has increased rapidly, so there is a tendency not to roughen the wiring as much as possible in order to improve dielectric properties. For such low-roughened or non-roughened wiring, adhesiveness is required more than conventional.

Also in this adhesiveness, the thermosetting resin composition described in Patent Document 1 described above cannot be said to be sufficient in recent years.

Further, it relates to a colored photosensitive resin composition, and includes a compound represented by a predetermined formula excellent in heat resistance and solvent properties (Patent Document 2). However, the photosensitive resin composition described in Patent Literature 2 is a photosensitive resin composition for color filters, and when used for a printed wiring board, the property capable of sufficiently maintaining adhesiveness under severe high temperature humidification conditions was not obtained.

Therefore, an object of the present invention is a curable resin composition suitable for use in printed wiring boards and the like, excellent in reliability and adhesion, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and the It is to provide a printed wiring board with cargo.

As a result of intensive research and development on a curable resin composition having excellent adhesion and reliability, the present inventors found that a cured product having high adhesion and reliability can be obtained by using a combination of a specific epoxy resin and a specific inorganic filler. It came to the completion of the invention.

The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin, (B-1) a photopolymerization initiator, (C) an epoxy resin having the following structural formula,

(D-1) It is characterized by containing an inorganic filler subjected to photoreactive surface treatment.

In addition, the curable resin composition of the present invention includes (A) a carboxyl group-containing resin, (B-2) a photobase generator, (C) an epoxy resin having the following structural formula,

(D-2) It is characterized by containing an inorganic filler subjected to a thermally reactive surface treatment.

In the curable resin composition of the present invention, the average particle diameter of the inorganic filler subjected to the surface treatment in (D-1) or (D-2) is 1.0 μm or less, and the maximum particle diameter is preferably 4.0 μm or less, (D) It is preferable that the compounding ratio of an inorganic filler is 25 to 80 mass %.

The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition to a film.

Further, the cured product of the present invention is characterized in that it is obtained by curing the curable resin composition or the resin layer of the dry film.

Moreover, the printed wiring board of this invention is characterized by having the said hardened|cured material.

According to the present invention, a cured product having excellent adhesion and reliability can be obtained.

The curable resin composition of the present invention comprises (A) a carboxyl group-containing resin and (C) an epoxy resin having the following structural formula

In addition to containing, (B-1) a photopolymerization initiator and (B-2) at least one of a photobase generator is included, and as an inorganic filler, when the photoreactive agent (B-1) is included, When the inorganic filler subjected to the surface treatment contains the photobase generator (B-2), each of the inorganic fillers subjected to the thermophotoreactive surface treatment is contained.

The curable resin composition of the present invention contains an epoxy resin having the specific structural formula described above. Since this epoxy resin has a low Gardner hue, that is, a high light transmittance, light reaches the deep portion of the film to which the curable resin composition is applied. Accordingly, in the case of a composition containing a photoreactive surface-treated inorganic filler, it can react with the surface treatment agent of the photoreactive surface-treated inorganic filler present in the deep portion of the film. Further, in the case of a composition containing a thermally reactive surface-treated inorganic filler, it can react with a surface treatment agent of the thermally reactive surface-treated inorganic filler by a photobase generator present in its core. Therefore, the cured product can be sufficiently cured even in the deep part, the moisture resistance is improved, and a cured product excellent in reliability and adhesion can be obtained.

Further, since the epoxy resin having the above specific structural formula has a hydrophobic and heat-resistant skeleton, a cured product having excellent moisture resistance and excellent reliability and adhesion can be obtained.

In addition, the epoxy resin having the above specific structural formula has a high glass transition temperature (Tg) in that it has a hydrophobic and heat-resistant skeleton, and has a low linear expansion coefficient in that it contains an inorganic filler, and has excellent cracking. It has resistance and has low warpage.

Further, since the epoxy resin having the above specific structural formula does not impair photoreactivity due to its low Gardner hue, the resin composition of the present invention has high resolution.

Based on these characteristics, it is considered that the cured product of the curable resin composition of the present invention has high adhesion and reliability.

Hereinafter, each component of the curable resin composition of the present invention will be described. In addition, in this specification, (meth)acrylate is a term generically referring to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[(A) Carboxyl group-containing resin]

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule can be used. Particularly, a photosensitive resin containing a carboxyl group having an ethylenically unsaturated double bond in the molecule is preferable from the viewpoint of photocurability and development resistance. It is preferable that the ethylenically unsaturated double bond is derived from acrylic acid or methacrylic acid or a derivative thereof. In the case of using only a carboxyl group-containing resin having no ethylenically unsaturated double bond, in order to make the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule described later, that is, a photoreactive monomer.

As a specific example of a carboxyl group-containing resin, the following compounds (all oligomers and polymers may be used) are mentioned.

(1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, and isobutylene.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate polyols, polyether polyols , Polyester-based polyol, polyolefin-based polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct diol, carboxyl group-containing urethane resin by polyaddition reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(3) Diisocyanate and bifunctional epoxy resins such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, and biphenol type epoxy resin A photosensitive urethane resin containing a carboxyl group by polyaddition reaction of a (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(4) During synthesis of the resin of (2) or (3) above, a compound having one hydroxyl group and one or more (meth)acryloyl groups is added in a molecule such as hydroxyalkyl (meth)acrylate, and the terminal (meth) ) Photosensitive urethane resin containing acrylated carboxyl groups.

(5) Compounds having one isocyanate group and one or more (meth)acryloyl groups in a molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate during the synthesis of the resin of (2) or (3) above. A carboxyl group-containing photosensitive urethane resin obtained by adding and terminating (meth)acrylate.

(6) A photosensitive resin containing a carboxyl group in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and a dibasic acid anhydride is added to the hydroxyl group present in the side chain.

(7) A photosensitive resin containing a carboxyl group in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin in which the hydroxyl group of a bifunctional (solid) epoxy resin is further epoxidized with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group. .

(8) A dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid is reacted with a difunctional oxetane resin, and a dibasic group such as phthalic anhydride, tetrahydro phthalic anhydride, and hexahydro phthalic anhydride is reacted with the primary hydroxyl group generated Carboxyl group-containing polyester resin to which an acid anhydride was added.

(9) In an epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and unsaturation such as (meth)acrylic acid Carboxyl group obtained by reacting a group-containing monocarboxylic acid and reacting polybasic acid anhydrides such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and adipic acid with respect to the alcoholic hydroxyl group of the obtained reaction product. Containing resin.

(10) A monocarboxylic acid containing an unsaturated group is reacted 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 and propylene oxide, and a polybasic acid anhydride is added to the reaction product. Carboxyl group-containing photosensitive resin obtained by reaction.

(11) A monocarboxylic acid containing an unsaturated group is reacted with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule and a cyclic carbonate compound such as ethylene carbonate and propylene carbonate, and a polybasic acid anhydride is added to the reaction product. Carboxyl group-containing photosensitive resin obtained by reaction.

(12) Carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11).

In addition, in this specification, (meth)acrylate is a term generically referring to acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

(A) It is preferable that the acid value of the carboxyl group-containing resin is 20-200 mgKOH/g. (A) When the acid value of the carboxyl group-containing resin is 20 to 200 mgKOH/g, formation of the pattern of the cured product becomes easy. More preferably, it is 50 to 130 mgKOH/g.

In addition, although the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally in the range of 2,000 to 150,000, and further preferably in the range of 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the developing resistance of the film at the exposed portion is improved, and the resolution is excellent. On the other hand, when the weight average molecular weight is 150,000 or less, the solubility of the unexposed portion is good, the resolution is excellent, and the storage stability is sometimes improved. The weight average molecular weight can be measured by gel permeation chromatography.

(A) The blending amount of the carboxyl group-containing resin is, for example, 10 to 60% by mass, preferably 20 to 60% by mass, based on the total amount of the curable resin composition excluding the solvent. By setting it as 10 mass% or more, preferably 20 mass% or more, the coating film strength can be improved. Moreover, by setting it as 60 mass% or less, viscosity becomes moderate and workability improves.

These carboxyl group-containing resins are not limited to those listed above, and can be used, and one type may be used alone, or multiple types may be mixed and used. Among them, carboxyl group-containing resins synthesized using a phenolic compound as a starting material, such as the carboxyl group-containing resins (10) and (11), are suitable because they are excellent in HAST test under high voltage, that is, B-HAST resistance or PCT resistance. Can be used.

[(B-1) Photoinitiator or (B-2) Photobase generator]

As the photoinitiator, any photoinitiator may be used as long as it is a photoinitiator known as a photoinitiator or a photoradical generator.

As a photoinitiator, for example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6- Dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4, Bisacylphosphine oxides such as 6-trimethylbenzoyl)-phenylphosphine oxide (Omnirad 819 manufactured by IGM Resins); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, blood Monoacylphosphine oxides such as isopropyl valeoylphenylphosphinate and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Omnirad TPO manufactured by IGM Resins); 1-hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- Hydroxyacetophenones such as 1-one; Benzoin, such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; Benzoin alkyl ethers; Benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2- Acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 2,4-di Thioxanthones such as isopropyl thioxanthone; Anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyloxime)],ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-car Oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- Titanocenes such as bis[2,6-difluoro-3-(2-(1-phyl-1-yl)ethyl)phenyl]titanium; Phenyl disulfide 2-nitrofluorene, butyloin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H -Carbazol-3-yl]-,1-(O-acetyloxime) is more preferred.

It is preferable that the compounding amount of a photoinitiator is 0.5-20 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resins. When it is 0.5 parts by mass or more, the surface hardenability becomes good, and when it is 20 parts by mass or less, halation is less likely to occur and good resolution is obtained.

The photobase generator is a compound that generates at least one basic substance capable of functioning as a catalyst for a thermosetting reaction by changing a molecular structure or cleaving a molecule by irradiation with light such as ultraviolet rays or visible light. As a basic substance, a secondary amine and a tertiary amine are mentioned, for example.

As the photobase generator, for example, α-aminoacetophenone compound, oxime ester compound, N-formylated aromatic amino compound, N-acylated aromatic amino compound, nitrobenzyl carbamate compound, alkoxybenzyl carbamate compound, etc. Can be mentioned. Among them, an oxime ester compound and an α-aminoacetophenone compound are preferable, and an oxime ester compound is more preferable, and ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -Yl]-,1-(O-acetyloxime) is more preferable. As the α-aminoacetophenone compound, it is particularly preferable to have two or more nitrogen atoms. Photobase generators may be used individually by 1 type, and may be used in combination of 2 or more types.

In addition, as a photobase generator, a quaternary ammonium salt etc. are mentioned.

As other photobase generators, WPBG-018 (brand name: 9-anthrylmethyl N,N'-diethylcarbamate), WPBG-027 (brand name: (E)-1-[3-(2-hydric) Roxyphenyl)-2-propenoyl]piperidine), WPBG-082 (trade name: guanidinium 2-(3-benzoylphenyl) propionate), WPBG-140 (trade name: 1-(anthraquinone-2) -Yl)ethyl imidazole carboxylate) etc. can also be used.

In addition, some of the substances of the photopolymerization initiator described above also function as a photobase generator. As the photopolymerization initiator which also functions as a photobase generator, an oxime ester photopolymerization initiator and an α-aminoacetophenone photopolymerization initiator are preferable.

It is preferable that the compounding amount of a photobase generator is 0.1-20 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resins. When it is 0.1 mass part or more, surface hardenability becomes favorable, and when it is 20 mass part or less, halation is hard to occur and good resolution is obtained.

[(C) Epoxy resin having a specific structural formula]

The curable resin composition of the present invention contains an epoxy resin having the following structural formula.

By including the epoxy resin having a low Gardner color, light can reach the core of the film, and a cured product having excellent adhesion and reliability can be obtained. Therefore, the curable resin composition of the present invention is suitable for use in printed wiring boards, which are required for reliability in high temperature and high humidity environments, among others, insulators for gauges or laminates used in semiconductor devices, and for semiconductor packages or vehicle mounting. Suitable for

Further, the curable resin composition contains the epoxy compound and an inorganic filler subjected to a specific surface treatment to be described later as essential components, thereby having crack resistance, excellent adhesion in a high temperature, high humidity environment, and the like.

The curable resin composition of the present invention, together with the epoxy resin having the (C) specific structural formula, to the extent that the effects peculiar to the present invention are not impaired, the (C) epoxy resin other than the epoxy resin having the specific structural formula may be included. I can. Epoxy resins other than the epoxy resin having the above (C) specific structural formula include epoxidized vegetable oil; Bisphenol A type epoxy resin; Hydroquinone type epoxy resin; Bisphenol type epoxy resin; Thioether type epoxy resin; Brominated epoxy resin; Novolak type epoxy resin; Biphenol novolak type epoxy resin; Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resin; Hydantoin type epoxy resin; Alicyclic epoxy resin; Trihydroxyphenylmethane type epoxy resin; Bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylolethane type epoxy resin; Heterocyclic epoxy resin; Diglycidylphthalate resin; Tetraglycidyl xylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resins having a dicyclopentadiene skeleton; Glycidyl methacrylate copolymerized epoxy resin; Copolymerization epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; CTBN-modified epoxy resin and the like can be mentioned, but the present invention is not limited thereto.

(C) The compounding amount of the epoxy resin having a specific structural formula is, for example, 1 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 60 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. Do. (C) When the compounding amount of the epoxy resin having a specific structural formula is 10 parts by mass or more, crack resistance and insulation reliability are more improved, and when it is 100 parts by mass or less, storage stability is improved.

[(D-1) Inorganic filler with photoreactive surface treatment or (D-2) Inorganic filler with thermally reactive surface treatment]

The curable resin composition of the present invention contains (D-1) an inorganic filler subjected to a photoreactive surface treatment or (D-2) an inorganic filler subjected to a thermally reactive surface treatment. By including the inorganic filler, the crack resistance of the cured product is further improved.

Here, by being a surface-treated inorganic filler, compatibility with (A) carboxyl group-containing resin or (C) epoxy resin can be improved.

In addition, (D-1) the curable resin composition of the present invention containing the inorganic filler subjected to photoreactive surface treatment, (B-1) the photopolymerization initiator is cleaved by transmitted light, and the photoreactive surface treatment is Since it reacts with the inorganic filler which has become, it is possible to improve the curability of the core of the film.

In addition, (D-2) the curable resin composition of the present invention containing an inorganic filler subjected to a thermally reactive surface treatment, (B-2) a photobase generator generates a base by transmitted light, Since it reacts with the surface-treated inorganic filler, it is possible to improve the curability of the core portion of the film.

Therefore, when the curable resin composition of the present invention contains (D-1) an inorganic filler subjected to a photoreactive surface treatment, (B-1) a photopolymerization initiator is included, and (D-2) a thermally reactive surface treatment is performed. When the inorganic filler which was made is included, (B-2) a photobase generator is included. In addition, as described above, since some substances of the photopolymerization initiator also function as photobase generators, there is no strict distinction between the photopolymerization initiator and the photobase generator.

The inorganic filler to be surface-treated is not particularly limited, and known and customary fillers, such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic Inorganic fillers such as mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc may be used. Among them, silica is preferred, and since the surface area is small and stress is dispersed throughout, it is more preferred that it is spherical silica in that it is difficult to become the origin of cracks.

Here, in the inorganic filler of (D-1), the surface-treated inorganic filler is a curable reactor that reacts with a photopolymerization initiator (B-1), and a surface treatment capable of introducing a photocurable reactor to the surface of the inorganic filler has been performed. In the inorganic filler of (D-2), as a curable reactor that reacts with the photobase generator (B-2), a surface treatment capable of introducing a thermosetting reactor to the surface of the inorganic filler has been performed. (D-1) Examples of the photocurable reactor of the inorganic filler subjected to the photoreactive surface treatment include a vinyl group, a styryl group, a methacrylic group, and an acrylic group. Especially, as a photocurable reactor, a methacrylic group, an acrylic group, and a vinyl group are preferable.

(D-2) Examples of the thermosetting reactor of the thermally reactive surface-treated inorganic filler include hydroxyl group, carboxyl group, isocyanate group, amino group, imino group, epoxy group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxy A methyl group, an ethoxyethyl group, an oxazoline group, etc. are mentioned. Among them, an amino group and an epoxy group are preferable.

In addition, the inorganic filler of (D-1) or the inorganic filler of (D-2) may have two or more types of curable reactive groups. (D) As the inorganic filler, surface-treated silica is preferable. By including the surface-treated silica, the CTE can be made low and the glass transition temperature can be made high.

(D) The method of introducing the curable reactor to the surface of the inorganic filler is not particularly limited, and may be introduced using a known and common method, and a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group may be used. Just treat the surface of the filler.

(D) As the surface treatment of the inorganic filler, surface treatment with a coupling agent is preferable. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Among them, a silane coupling agent is preferable.

As the silane coupling agent, (D) a silane coupling agent capable of introducing a curing reactive group into the inorganic filler is preferable. Examples of the silane coupling agent capable of introducing a thermosetting reactive group include a silane coupling agent having an epoxy group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling agent having an isocyanate group. Among them, a silane having an epoxy group The coupling agent is more preferable. As the silane coupling agent capable of introducing a photocurable reactive group, a silane coupling agent having a vinyl group, a silane coupling agent having a styryl group, a silane coupling agent having a methacrylic group, and a silane coupling agent having an acrylic group are preferable. A silane coupling agent is more preferable.

The inorganic filler of (D-1) or (D-2) may be blended in the curable resin composition of the present invention in a surface-treated state, and the inorganic fillers in the composition are mixed with each of the untreated inorganic filler and the surface treatment agent. Although it may be surface-treated, it is preferable to mix|blend the inorganic filler which surface-treated beforehand. By blending the inorganic fillers subjected to surface treatment in advance, it is possible to prevent a decrease in crack resistance and the like due to the surface treatment agent not consumed in the surface treatment that may remain in the case of each blending. In the case of surface treatment in advance, it is preferable to blend a pre-dispersion obtained by pre-dispersing the (D) inorganic filler in the solvent or resin component, and pre-disperse the surface-treated inorganic filler in a solvent, and blend the pre-dispersion liquid into the composition. , When pre-dispersing the surface-untreated inorganic filler in a solvent, it is more preferable to sufficiently surface-treat the surface, and then mix the pre-dispersion into the composition.

In the curable resin composition of the present invention, the inorganic filler of (D-1) or the inorganic filler of (D-2) preferably has an average particle diameter of 1 µm or less from the viewpoint of more excellent crack resistance. More preferably, it is 0.8 micrometers or less. In addition, in this specification, the average particle diameter means the value of D50, and is a value measured using the Nikkiso Microtrac particle size analyzer, for example.

In addition, the inorganic filler of (D-1) or the inorganic filler of (D-2) having a maximum particle diameter of 4.0 µm or less is preferable in that it reacts efficiently and is more excellent in crack resistance and adhesion. More preferably, it is 3.0 micrometers or less. In addition, in this specification, the maximum particle diameter refers to the value of D100, and is a value measured using the Nikkiso Microtrack particle size analyzer, for example.

The blending amount of the inorganic filler is preferably 25 to 85% by mass, more preferably 30 to 75% by mass, and still more preferably 35 to 70% by mass per total solid content of the curable resin composition.

As a photopolymerizable oligomer, an unsaturated polyester type oligomer, a (meth)acrylate type oligomer, etc. are mentioned. Examples of (meth)acrylate oligomers include epoxy (meth)acrylates such as phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, bisphenol-type epoxy (meth)acrylate, and urethane (meth) Acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, polybutadiene-modified (meth)acrylate, and the like.

As a photopolymerizable vinyl monomer, it is a well-known thing, for example, styrene derivatives, such as styrene, chlorostyrene, and α-methylstyrene; Vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl Vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; Acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc. Meth)acrylamides; Allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isoboronyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth) ) Esters of (meth)acrylic acid such as acrylate; Hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri (meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, trimethylolpropanetri(meth)acrylate , Alkylene polyol poly(meth)acrylate such as pentaerythritol tetra(meth)acrylate and dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(s) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc. Meth)acrylates; Poly(meth)acrylates such as hydroxypivalate neopentyl glycol ester di(meth)acrylate; Isocyanurate type poly(meth)acrylates, such as tris[(meth)acryloxyethyl]isocyanurate, etc. are mentioned. These can be used alone or in combination of two or more according to the required characteristics.

The compounding amount of the compound having an ethylenically unsaturated bond is preferably 3 to 40 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A). When it is 3 mass parts or more, surface hardenability is improved, and when it is 40 mass parts or less, halation is suppressed. More preferably, it is 5 to 30 mass parts.

(Thermal curing catalyst)

It is preferable that the curable resin composition of this invention contains a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole , Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine Hydrazine compounds such as compounds, adipic acid dihydrazide, and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine/isocyanuric acid S-triazine derivatives such as adducts can also be used, and preferably these compounds which also function as adhesion-imparting agents are used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is preferably 0.05 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the (C) epoxy resin.

(Hardener)

The curable resin composition of the present invention may contain a curing agent. As a curing agent, a phenol resin, a polycarboxylic acid, and its acid anhydride, a cyanate ester resin, an active ester resin, a maleimide compound, an alicyclic olefin polymer, etc. are mentioned. The curing agent may be used alone or in combination of two or more.

The curing agent is (C) a functional group capable of thermosetting reaction such as an epoxy group of a thermosetting resin such as an epoxy resin, and the ratio of the functional group in the curing agent reacting with the functional group is the functional group of the curing agent/the functional group capable of thermosetting reaction (equivalent ratio) = It is preferable to blend in a ratio of 0.2 to 3. By setting it as the said range, the balance of storage stability and hardenability is excellent.

(coloring agent)

The curable resin composition of the present invention may contain a colorant. As the colorant, a known colorant such as red, blue, green, yellow, black, and white can be used, and any of a pigment, a dye, and a dye may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

The amount of the colorant to be added is not particularly limited, but a ratio of preferably 10 parts by mass or less, particularly preferably 0.1 to 7 parts by mass per 100 parts by mass of the (A) carboxyl group-containing resin is sufficient.

(Organic solvent)

The curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or carrier film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether Glycol ethers such as acetate and tripropylene glycol monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; Known and common organic solvents, such as petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional ingredients)

Further, the curable resin composition of the present invention may be blended with other known and commonly used additives in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial/antifoaming agents, defoaming agents, leveling agents, thickeners, adhesion imparting agents, thixotropic agents, photo-initiating aids. , A sensitizer, a thermoplastic resin, an organic filler, a releasing agent, a surface treatment agent, a dispersant, a dispersion aid, a surface modifier, a stabilizer, a phosphor, and the like.

The curable resin composition of the present invention may contain a thermosetting resin other than (C) an epoxy resin within a range that does not impair the effects of the present invention. The thermosetting resin may be a resin curing by heating to exhibit electrical insulation, and examples thereof include epoxy compounds other than (C) epoxy resins, oxetane compounds, melamine resins, and silicone resins, and these may be used in combination.

The curable resin composition of the present invention may be used as a dry film or may be used as a liquid. In the case of using as a liquid, one liquid or two or more liquids may be used.

Next, the dry film of this invention has a resin layer obtained by apply|coating and drying the curable resin composition of this invention on a carrier film. When forming a dry film, first, the curable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and then comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater , A gravure coater, a spray coater or the like is applied to the carrier film with a uniform thickness. Thereafter, the applied composition is dried for 1 to 30 minutes at a temperature of usually 40 to 130°C, whereby a resin layer can be formed. There is no restriction|limiting in particular about the coating film thickness, It is generally the film thickness after drying, and is suitably selected from 3 to 150 micrometers, Preferably it is 5 to 60 micrometers.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, In general, it is suitably selected in the range of 10 to 150 micrometers. It is more preferably in the range of 15 to 130 μm.

After forming a resin layer containing the curable resin composition of the present invention on a carrier film, for the purpose of preventing dust from adhering to the surface of the resin layer, a peelable cover film is further laminated on the surface of the resin layer. It is desirable. As a peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used. As the cover film, when peeling the cover film, what is necessary is just to be smaller than the adhesive force of a resin layer and a carrier film.

Further, in the present invention, a resin layer may be formed by applying and drying the curable resin composition of the present invention on the cover film, and a carrier film may be laminated on the surface thereof. That is, when manufacturing a dry film in this invention, as a film to which the curable resin composition of this invention is applied, you may use either a carrier film and a cover film.

The printed wiring board of the present invention has a cured product obtained from the curable resin composition of the present invention or a resin layer of a dry film. As a manufacturing method of the printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the application method using the organic solvent, and then dip coating method, flow coating method, roll coating method on a substrate. After coating by a method such as a method, a bar coater method, a screen printing method, a curtain coating method, or the like, the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100°C to form a touch-drying resin layer. To form. Further, in the case of a dry film, a resin layer is formed on the substrate by peeling the carrier film after bonding on the substrate so that the resin layer is in contact with the substrate by a laminator or the like.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/nonwoven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin Materials such as copper-clad laminates for high-frequency circuits using polyethylene·polyphenylene ether, polyphenylene oxide·cyanate, etc. are used, copper clad laminates of all grades (FR-4, etc.), other metal substrates, polyimide films , PET film, polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate, and the like.

The volatilization drying performed after applying the curable resin composition of the present invention is a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. (with a heat source of an air heating method by steam, the hot air in the dryer is counterflowed. It can be carried out using a method of contacting and a method of spraying from a nozzle to the support).

After forming the resin layer on the printed wiring board, it is selectively exposed with an active energy ray through a photomask having a predetermined pattern, and the unexposed part is a dilute alkali aqueous solution (e.g., 0.3 to 3% by mass aqueous sodium carbonate solution). ) To form a pattern of the cured product. In addition, by irradiating the cured product with active energy rays and then heat curing (for example, 100 to 220°C), or by irradiating with active energy rays after heat curing, or by final curing (main curing) only by heat curing It forms a cured film excellent in various properties such as.

In addition, when the curable resin composition of the present invention contains a photobase generator, it is preferable to heat before development after exposure, and as a heating condition before development after exposure, for example, heating at 60 to 150°C for 1 to 60 minutes It is desirable.

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc. may be mounted, and a device that irradiates ultraviolet rays in the range of 350 to 450 nm may be used, and a direct drawing device (For example, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer) can also be used. As the lamp light source or the laser light source of the direct writing machine, the maximum wavelength may be in the range of 350 to 450 nm. Light exposure for image formation film varies, depending upon the thickness, but in general can be within the 10 to 1000mJ / cm ^2, preferably in the range of 20 to a range of 800mJ / cm ^2.

As the above developing method, a dipping method, a shower method, a spray method, a brush method, etc. can be used, and as a developer, an alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc. Can be used.

The curable resin composition of the present invention is suitably used to form a cured film on a printed wiring board, more suitably, used to form a permanent film, and more suitably, to form a solder resist, an interlayer insulating layer, and a coverlay. It is used to In addition, according to the curable resin composition of the present invention, since a cured product having excellent crack resistance and insulation reliability can be obtained, a printed wiring board having a fine pitch wiring pattern requiring high reliability, for example, a package substrate, In particular, it can be used suitably for the formation of permanent films for FC-BGA (especially solder resists).

[Example]

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, all of "parts" and "%" below are based on mass unless otherwise noted.

Each component shown in Tables 1 to 3 was blended in the proportions shown in Tables 1 to 3, premixed with a stirrer, and then kneaded with a 3-axis roll mill to prepare curable resin compositions of Examples 1 to 20 and Comparative Examples 1 to 5 I did. Various properties were evaluated for the obtained curable composition, and the results are listed in Tables 1 to 3.

The alkali developable resins in Tables 1 to 3 were prepared as follows.

[(A-1) Synthesis of alkali developable resin]

Into an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device and a stirring device, 119.4 parts of a novolac cresol resin (Shonol CRG951 manufactured by Showa Denko, OH equivalent: 119.4), 1.19 parts of potassium hydroxide and 119.4 parts of toluene were introduced. Then, the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide was gradually added dropwise, and reacted at 125 to 132°C and 0 to 4.8 kg/cm ² for 16 hours. Then, it cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to this reaction solution, and potassium hydroxide was neutralized, and the novolac type cresol of 62.1% non-volatile matter and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.) A propylene oxide reaction solution of resin was obtained. This was obtained by adding an average of 1.08 mol of propylene oxide per equivalent of phenolic hydroxyl groups.

293.0 parts of the propylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer and an air suction tube, and air was introduced into 10 ml. It was blown at a rate of /min, and reacted at 110°C for 12 hours while stirring. The water produced by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water flowed out. Then, it cooled to room temperature, and the obtained reaction solution was neutralized with 35.35 parts of 15% sodium hydroxide aqueous solution, and then washed with water. Thereafter, toluene was distilled off while replacing 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolac-type acrylate resin solution. Then, 332.5 parts of the obtained novolac-type acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air intake tube, and air was blown at a rate of 10 ml/min, while stirring tetrahydrophthalic acid. 60.8 parts of anhydrides were gradually added, reacted at 95 to 101°C for 6 hours, cooled, and then taken out. In this way, a solution of the photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and an acid value of the solid content of 87.7 mgKOH/g was obtained. Hereinafter, the solution of this carboxyl group-containing photosensitive resin is called resin solution A-1.

[(A-2) Synthesis of alkali developable resin]

Diethylene glycol monoethyl ether acetate 600 g to orthocresol novolak type epoxy resin (DIC company EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5.0 mol), acrylic acid 360 g (5.0 mol), and hydroquinone 1.5 g were added, heated and stirred at 100°C, and dissolved uniformly.

Subsequently, 4.3 g of triphenylphosphine was added, heated to 110°C and reacted for 2 hours, and then heated to 120°C and further reacted for 12 hours. To the obtained reaction solution, 415 g of an aromatic hydrocarbon (Sorbetso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, followed by reaction at 110° C. for 4 hours, followed by cooling to obtain a photosensitive carboxyl group-containing resin solution. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 89 mgKOH/g. Hereinafter, the solution of this carboxyl group-containing photosensitive resin is called resin solution A-2.

[(A-3) Synthesis of alkali developable resin]

In a flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 325.0 parts of dipropylene glycol monomethyl ether as a solvent are heated to 110° C., 174.0 parts of methacrylic acid, ε-caprolactone-modified methacrylic acid (average molecular weight 314) A mixture of 174.0 parts, 77.0 parts of methyl methacrylate, 222.0 parts of dipropylene glycol monomethyl ether, and 12.0 parts of t-butylperoxy2-ethylhexanoate (perbutyl O manufactured by Nichi Corporation) as a polymerization catalyst was prepared over 3 hours. It was dripped and stirred at 110 degreeC for 3 hours more, the polymerization catalyst was deactivated, and a resin solution was obtained.

After cooling this resin solution, 289.0 parts of Cychroma A200, manufactured by Daicel Chemical Industries, Ltd., 3.0 parts of triphenylphosphine, and 1.3 parts of hydroquinone monomethyl ether were added, the temperature was raised to 100° C., and the addition reaction of the ring opening of the epoxy group was stirred. And a photosensitive carboxyl group-containing resin solution was obtained.

The resin solution thus obtained had a weight average molecular weight (Mw) of 15,000, a solid content of 57%, and an acid value of a solid product of 79.8 mgKOH/g. Hereinafter, the solution of this carboxyl group-containing photosensitive resin is called resin solution A-3.

In Tables 1 to 3, the photoinitiators are as follows.

(B-1.1): Omnirad (Omniard) TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins

(B-1, B-2.1): Omnirad (Omniard) 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one manufactured by IGM Resins)

(B-1, B-2.1): Irgacure OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(manufactured by BASF Japan) o-acetyloxime)

(B-2.1): Wako Junyaku Corporation WPBG-082 (guanidinium 2-(3-benzoylphenyl) propionate)

In Tables 1 to 3, the special epoxy resin which is an epoxy resin having a specific structural formula (C) of the present invention is as follows.

(C-1): Epoxy resin having the following skeleton (epoxy equivalent 210)

(C-2): Epoxy resin having the above skeleton (epoxy equivalent 232)

In addition, the cured resin composition of Tables 1 to 3 may contain the following epoxy resins (C-3) to (C-6) as epoxy resins other than the epoxy resin containing the (C) specific structural formula.

(C-3) Alicyclic epoxy resin having the following skeleton (epoxy equivalent 96)

(C-4) DEN431 (phenol novolac epoxy resin) manufactured by Dow Chemical

(C-5) DIC N-870 75EA (bisphenol A novolac type epoxy resin)

(C-6) DIC Corporation HP-7241 (trisphenol methane type epoxy resin)

[(D-1.1) Inorganic treatment → Preparation of methacrylsilane treated silica slurry]

After 50 g of a water slurry of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm) was heated to 70° C., a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, aged for 30 minutes, and while maintaining the pH at 7±1 with hydrochloric acid, a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 5% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. Silica solvent dispersion obtained by uniformly dispersing 50 g of silica particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) I got my arms.

[(D-1.2) Inorganic treatment → Preparation of methacrylsilane treatment barium sulfate slurry]

After the water slurry of 50 g of barium sulfate particles (precipitated barium 100 manufactured by Sakai Chemical Co., Ltd.) was heated to 70°C, a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, aged for 30 minutes, and while maintaining the pH at 7±1 with hydrochloric acid, a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 5% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid material of barium sulfate particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. A silica solvent in which 50 g of barium sulfate particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) are uniformly dispersed A dispersion was obtained.

[(D-1.3) Preparation of methacrylsilane treated silica slurry]

50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed A silica solvent dispersion was obtained.

[(D-1.4) Adjustment of acrylic silane treated silica slurry]

Silica obtained by uniformly dispersing 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an acrylic group (KBM-5103 manufactured by Shin-Etsu Chemical Co., Ltd.) A solvent dispersion was obtained.

[(D-1.5) Adjustment of vinylsilane treated silica slurry]

Silica obtained by uniformly dispersing 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a vinyl group (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) A solvent dispersion was obtained.

[(D-1.6) Inorganic treatment → Preparation of methacrylsilane treated silica slurry]

After 50 g of a water slurry of spherical silica particles (SFP-20M manufactured by Denka Corporation, average particle diameter: 400 nm) was heated to 70°C, a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, aged for 30 minutes, and while maintaining the pH at 7±1 with hydrochloric acid, a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 5% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. Silica solvent dispersion obtained by uniformly dispersing 50 g of silica particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having a methacrylic group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) I got my arms.

[(D-2.1) Inorganic treatment → adjustment of epoxy silane treated silica slurry]

After 50 g of a water slurry of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm) was heated to 70° C., a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, aged for 30 minutes, and while maintaining the pH at 7±1 with hydrochloric acid, a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 5% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid substance of silica particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. A silica solvent dispersion obtained by uniformly dispersing 50 g of silica particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) Got it.

[(D-2.2) Inorganic Treatment → Adjustment of Epoxysilane Treatment Barium Sulfate Slurry]

After the water slurry of 50 g of barium sulfate particles (precipitated barium 100 manufactured by Sakai Chemical Co., Ltd.) was heated to 70°C, a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, aged for 30 minutes, and while maintaining the pH at 7±1 with hydrochloric acid, a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 5% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid material of barium sulfate particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. Silica solvent dispersion obtained by uniformly dispersing 50 g of barium sulfate particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) I got my arms.

[(D-2.3) Preparation of epoxy silane treated silica slurry]

Silica obtained by uniformly dispersing 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) A solvent dispersion was obtained.

[(D-2.4) Preparation of amino-treated silica slurry]

Silica obtained by uniformly dispersing 50 g of spherical silica particles (SO-C2 manufactured by Admatex, average particle diameter: 500 nm), 48 g of PMA as a solvent, and 2 g of a silane coupling agent having an acrylic group (KBM-573 manufactured by Shin-Etsu Chemical Co., Ltd.) A solvent dispersion was obtained.

[(D-3) Preparation of silica slurry]

A silica solvent dispersion product obtained by uniformly dispersing 50 g of spherical silica particles (SO-C2 by Admatex, average particle diameter: 500 nm), 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111) were uniformly dispersed.

[(D-4) Preparation of inorganic treated barium sulfate slurry]

After the water slurry of 50 g of barium sulfate particles (precipitated barium 100 manufactured by Sakai Chemical Co., Ltd.) was heated to 70°C, a 10% aqueous sodium silicate solution was added to the silica particles by 1% in terms of silica particles. Hydrochloric acid was added to the slurry to adjust the pH to 4, aged for 30 minutes, and while maintaining the pH at 7±1 with hydrochloric acid, a 20% sodium aluminate (NaAlO ₂ ) aqueous solution was added to the silica particles with alumina (Al ₂ O). ₃ ) It added 5% in conversion. Thereafter, a 20% aqueous sodium hydroxide solution was added, the pH was adjusted to 7, and the mixture was aged for 30 minutes. Thereafter, the slurry was filtered with water by a filter press and dried under vacuum to obtain a solid material of barium sulfate particles coated with a hydrated oxide of silicon and a hydrated oxide of aluminum. A silica solvent dispersion product obtained by uniformly dispersing 50 g of barium sulfate particles coated with a hydrated oxide of silicon obtained in the same manner as above, 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111) were obtained.

[(D-5) Adjustment of barium sulfate slurry]

A barium sulfate solvent dispersion obtained by uniformly dispersing 50 g of barium sulfate particles (precipitated barium 100 manufactured by Sakai Chemical Co., Ltd.), 48 g of PMA as a solvent, and 2 g of a dispersant (BYK-111) were obtained.

In addition, the cured resin composition of Tables 1-3 may contain the following components.

DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Corporation

・CZ-601D (blue colorant) manufactured by Nikko Bikkus

・CZ-309D (yellow colorant) manufactured by Nikko Bikkus

DICY (dicyandiamide)

(Production of dry film)

The curable resin compositions of each of the Examples and Comparative Examples shown in Tables 1 to 3 pass through a drying furnace of 60 to 120°C at 10 m/min on PET using a die coater for each of the Examples and Comparative Examples. Then, a dry film was obtained by volatilizing a solvent.

(Production of standard evaluation board)

The dry film obtained by the above method was laminated on a test substrate using a vacuum laminator CVP-300 (manufactured by Nikko Materials) to obtain a laminate of a photosensitive resin composition. Pattern exposure was performed according to the evaluation item so that the number of hardening stages of 10 stages with a Stouffer 41 stage step tablet using DXP-3580 (ORC company make, ultra-high pressure mercury lamp DI exposure machine) for this laminated body. After 10 minutes after exposure, the PET film was peeled off, and development was performed with a 30° C. 1% by mass sodium carbonate aqueous solution with a development time equal to twice the breakpoint (shortest development time). Thereafter, an evaluation substrate was obtained by exposure with a UV conveyor (manufactured by ORC, a metal halide lamp) at a cumulative exposure amount of 2000 mJ/cm ² , and curing at 170° C. for 60 minutes in a thermal circulation type box furnace.

<Glass transition temperature Tg>

On the copper foil substrate, each curable resin composition was formed so as to have a film thickness of about 40 µm, and exposure was performed in a rectangular pattern of 50 mm x 3 mm. Thereafter, development and curing were performed under the same conditions as for the preparation of the standard evaluation substrate.

The cured film of the evaluation substrate obtained by the above was peeled off from the copper foil and evaluated. Measurement was performed using a TMA measuring device (model name: TMA6000 manufactured by Shimadzu Corporation), and Tg was evaluated. The evaluation criteria are as follows.

◎… 180℃ or higher

○… 170℃ or more and less than 180

△... 160℃ or more and less than 170

×… Less than 160℃

<Toughness evaluation (production of copper foil substrate with resin layer)>

On the copper foil substrate, the curable resin composition was formed so as to have a film thickness of about 40 µm, and exposure was performed in a rectangular pattern of 80 mm x 10 mm. Thereafter, development and curing were performed under the same conditions as for the preparation of the standard evaluation substrate.

The cured film of the evaluation substrate obtained by the above was peeled off from the copper foil and evaluated. The measurement was performed using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation), and evaluated for the maximum stress or elongation at break. The evaluation criteria are as follows.

◎… Maximum point stress 80 MPa or more or Elongation at break 6% or more

○… Maximum point stress 70 MPa or more and less than 80 MPa, or Elongation at break 4% or more and less than 6%

△... Maximum point stress 50 MPa or more and less than 70 MPa, Elongation at break 2% or more and less than 4%

×… Maximum stress less than 50 MPa, or less than 2% elongation at break

<Bending>

Each curable resin composition was formed so as to have a film thickness of about 20 µm on a 35 µm copper foil substrate treated in CZ-8101B under conditions of an etching rate of 1.0 µm/m ² , and the entire surface was exposed. Then, development and hardening were performed under predetermined conditions.

The cured film of the evaluation substrate obtained as described above was cut out into 50 mm x 50 mm, and the cured film faced downward and left on a horizontal stand. After standing, the distance from the horizontal stand to the Cu foil was measured to measure the amount of warpage.

◎… Less than 10mm

○… 10mm or more, less than 15mm

△... 15mm or more, less than 20mm

×… Less than 20mm

<Low-profile adhesion-initial adhesion>

A curable resin composition was formed on the copper foil treated in CZ-8201B under the conditions of an etching rate of 0.5 µm/m ² to have a film thickness of about 20 µm, and the entire surface was exposed. Thereafter, development and curing were performed under the same conditions as for the preparation of the standard evaluation substrate previously determined. Thereafter, a thermosetting adhesive araldite (manufactured by Nichireflective) was formed on the surface of the curable resin composition, adhered to the FR-4 substrate, and cured at 80°C for 6 hours. After that, the evaluation substrate was cut at intervals of 20 mm, and both sides were peeled off so that the Cu foil width became 10 mm wide to prepare an evaluation strip. This evaluation strip was subjected to a 90° peeling test using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation) to evaluate adhesion. The evaluation criteria are as follows.

◎: 6.0N/cm or more

○: 5.0 or more and less than 6.0 N/cm

△: 4.0 or more and less than 5.0 N/cm

×: less than 4.0 N/cm

<Low profile adhesion-Adhesion after 50h of HAST>

A curable resin composition was formed on the copper foil treated in CZ-8201B under the conditions of an etching rate of 0.5 µm/m ² to have a film thickness of about 20 µm, and the entire surface was exposed. Thereafter, development and curing were performed under the same conditions as for the preparation of the standard evaluation substrate. Thereafter, a thermosetting adhesive araldite (manufactured by Nichireflective) was formed on the surface of the curable resin composition, adhered to the FR-4 substrate, and cured at 80°C for 6 hours. Thereafter, the evaluation substrate was cut at intervals of 20 mm, and both sides were peeled off so that the Cu foil width became 10 mm wide to prepare an evaluation strip. This evaluation strip was treated at 130°C and 85% for 50 h, and a 90° peel test was performed using a tensile tester (model name: AGS-G 100N manufactured by Shimadzu Corporation) to evaluate adhesion. The evaluation criteria are as follows.

◎: 5.0N/cm or more

○: 4.0 or more and less than 5.0 N/cm

△: 3.0 or more and less than 4.0 N/cm

×: less than 3.0N/cm

<Resolution evaluation>

On a plated copper substrate treated with CZ-8101B under conditions of an etching rate of 1.0 µm/m ² , a curable resin composition was formed to have a film thickness of about 20 µm, and exposure was performed with various opening patterns. Thereafter, development and evaluation were performed under the same conditions as those of the standard evaluation substrate.

The opening diameter of the evaluation substrate obtained as described above was observed, and it was confirmed that there was no occurrence of halation or undercut, and evaluation was performed.

◎… Good opening diameter at 60㎛

○… Good aperture diameter at 70㎛

△... Good opening diameter at 80㎛

×… Good aperture diameter is not obtained at 80㎛ or development is impossible

<HAST resistance>

In CZ-8101B, a curable resin composition was formed to have a film thickness of about 20 μm on a substrate on which a comb-shaped pattern of L/S=20/20 μm was formed, which was treated under the condition of an etching rate of 1.0 μm/m ² , and the entire surface was exposed. I did. Thereafter, development and curing were performed under the same conditions as for the preparation of the standard evaluation substrate.

After that, the electrodes were connected and the HAST test was conducted under the conditions of 130℃, 85%, and 5V.

◎: 400h pass

○: 350h pass

△: 300h pass

×: NG within 250h

<TCT tolerance>

On the package substrate treated in CZ-8101B under the conditions of an etching rate of 1.0 µm/m ² , a curable resin composition was formed so as to have a Cu phase film thickness of about 18 µm, and SRO 80 µm exposure was performed on a copper pad. Thereafter, development and curing were performed under the same conditions as for the preparation of the standard evaluation substrate. After that, Au plating treatment, solder bump formation, and Si chip were mounted to obtain an evaluation substrate.

The evaluation substrate obtained as described above was placed in a cooling/heat cycle machine in which a temperature cycle was performed between -65°C and 150°C, and a thermal cycle test (TCT) was performed. Then, the surface of the cured film at 600 cycles, 800 cycles and 1000 cycles was observed. The judgment criteria are as follows.

◎: No abnormality in 1000 cycles

○: No abnormality in 800 cycles, cracking in 1000 cycles

△: No abnormality in 600 cycles, cracking in 800 cycles

×: Crack occurs in 600 cycles

From the results shown in Tables 1 to 3, it can be seen that the cured products of the curable resin compositions of Examples 1 to 20 of the present invention are excellent in crack resistance, insulation reliability, and adhesion. In contrast, when the curable resin compositions of Comparative Examples 1 to 5 were used, adhesion was poor and it was difficult to obtain insulation reliability.

Claims (7)

(A) a carboxyl group-containing resin,
(B-1) a photoinitiator,
(C) an epoxy resin having the following structural formula,

(D-1) Inorganic filler with photoreactive surface treatment
Curable resin composition characterized in that it contains. (A) a carboxyl group-containing resin,
(B-2) a photobase generator, and
(C) an epoxy resin having the following structural formula,

(D-2) Inorganic filler with heat-reactive surface treatment
Curable resin composition characterized in that it contains. The curable resin composition according to claim 1 or 2, wherein the surface-treated inorganic filler has an average particle diameter of 1.0 µm or less and a maximum particle diameter of 4.0 µm or less. The curable resin composition according to claim 1 or 2, wherein the blending ratio of the surface-treated inorganic filler is 25 to 80% by mass. A dry film comprising a resin layer obtained by applying and drying the curable resin composition according to claim 1 or 2 to a film. A cured product obtained by curing the resin layer of a dry film having a resin layer obtained by applying the curable resin composition according to claim 1 or 2 or the curable resin composition to a film and drying it. A printed wiring board comprising the cured product according to claim 6.