JP6723788B2 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Description

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

Due to the rapid progress of semiconductor parts in recent years, electronic devices tend to be smaller and lighter, have higher performance, and have more functions. Following this trend, the density of printed wiring boards and the surface mounting of components are also increasing. In the production of high-density printed wiring boards, a photosensitive composition is generally used for forming a solder resist or the like, and dry film type compositions and liquid compositions have been developed. Among these, an alkali developing type photosensitive composition using a dilute alkaline aqueous solution as a developing solution has become mainstream from the viewpoint of environmental problems, and several composition systems have been proposed in the past. For example, Patent Document 1 describes a photosensitive composition containing a specific active energy ray-curable resin, a photopolymerization initiator and a diluent. Further, Patent Document 2 includes an alkali-soluble resin, a heat-reactive compound and a photobase generator, and the alkali-soluble resin and the heat-reactive compound are subjected to an addition reaction by selective light irradiation, whereby alkali development is performed. A resin composition capable of forming a negative pattern is described.

In recent years, IC packages, even among printed wiring boards, are becoming lighter, thinner and smaller due to the rise of smartphones and tablet PCs.

Japanese Patent Laid-Open No. 61-243869 (claims) WO2013/172435A1 (Claims)

As the IC package becomes lighter, thinner, shorter, and smaller, a photosensitive composition used for a solder resist of the IC package needs to have a narrower space between lines and an opening diameter, and therefore, more excellent resolution is required.

Then, the objective of this invention is providing the curable resin composition which can obtain the hardened|cured material excellent in resolution, a dry film, hardened|cured material, and a printed wiring board.

In order to solve the above problems, the present inventors have studied using a photosensitive composition that utilizes photopolymerization, such as the photosensitive composition described in Patent Document 1, but it has been found that Progression, that is, halation is likely to occur, and there is a limit to improvement of resolution.

In addition, in the case of the resin composition described in Patent Document 2, since an organic compound having an ethylenically unsaturated group is not required, reliability (PCT resistance) is improved, and halation is unlikely to occur, but the resin composition does not develop after development. It was found that the pattern flowed slightly and the pattern collapsed (this is called resin flow). This phenomenon remarkably occurs especially when heat treatment is performed. Then, when the pattern becomes fine, the collapse of the pattern causes a large deviation between the lines and the size of the opening from the designed value, which hinders the improvement of the resolution.

As a result of further studies by the present inventors, an alkali-soluble resin having an ethylenically unsaturated group introduced, a specific photopolymerization initiator, a thermosetting component, and a filler are contained, and the ethylenically unsaturated group is substantially contained. It was found that the above problems can be solved by using a curable resin composition that does not contain an organic compound having an ethylenically unsaturated group in addition to the alkali-soluble resin having the above, and has completed the present invention.

That is, the curable resin composition of the present invention comprises (A) an alkali-soluble resin having an ethylenically unsaturated group, (B) at least two photopolymerization initiators that do not generate a base, (C) a thermosetting component, and ( D) A resin composition containing a filler, which is characterized by containing substantially no (A) an organic compound having an ethylenically unsaturated group other than the above-mentioned (A) soluble in alkali developing having an ethylenically unsaturated group. Is.

The curable resin composition of the present invention comprises (B1) an acylphosphine oxide-based photopolymerization initiator and (B2) a titanocene-based photopolymerization initiator as at least two photopolymerization initiators that do not generate the base (B). It is preferable to include.

The curable resin composition of the present invention preferably contains the filler (D) in an amount of 30 to 90 mass% in the solid content of the curable resin composition.

The curable resin composition of the present invention preferably contains a surface-treated filler as the (D) filler.

In the curable resin composition of the present invention, the surface treatment filler is preferably silica having an ethylenically unsaturated group.

The dry film of the present invention has a resin layer obtained from the curable resin composition.

The cured product of the present invention is characterized by being obtained by curing the curable resin composition or the resin layer of the dry film.

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

According to the present invention, it is possible to provide a curable resin composition, a dry film, a cured product, and a printed wiring board that can provide a cured product having excellent resolution.

The curable resin composition of the present invention comprises (A) an ethylenically unsaturated group-containing alkali-soluble resin (hereinafter sometimes abbreviated as (A) alkali-soluble resin) and (B) at least 2 which does not generate a base. A curable resin composition containing two kinds of photopolymerization initiators (hereinafter sometimes abbreviated as (B) at least two kinds of photopolymerization initiators), (C) a thermosetting component, and (D) a filler. It is characterized in that it does not contain (E) an organic compound having an ethylenically unsaturated group other than the alkali-soluble resin having substantially (A) an ethylenically unsaturated double bond. The curable resin composition of the present invention enables negative pattern formation by alkali development by selective light irradiation. Here, the term “pattern formation” means formation of a patterned cured product, that is, a pattern layer.
The curable resin composition of the present invention preferably contains a surface-treated filler (that is, a surface-treated filler) as the (D) filler, and the surface-treated filler more preferably has an ethylenically unsaturated group. .. Here, when the surface treatment filler has an ethylenically unsaturated group, the curable resin composition of the present invention does not substantially contain (E) an organic compound having an ethylenically unsaturated group, which is an ethylenically unsaturated group. The surface-treated filler having a group is not included.

In the curable resin composition of the present invention, the detailed mechanism is not clear, but (E) an ethylenically unsaturated group-containing organic compound other than substantially (A) an ethylenically unsaturated group-containing alkali-soluble resin. It is considered that halation is unlikely to occur by not containing it. Further, when a photopolymerization initiator that generates a base is used, the sensitivity is too high and the curing reaction proceeds, so that there is a limit to the improvement of resolution, but two photopolymerization initiators that do not generate a base. The resolution could be improved by blending.

Further, in the curable resin composition of the present invention, a surface-treated filler is further used as the (D) filler, and the blending amount of the (D) filler is 30 to 90% by mass in the solid content to obtain a cured product. The elastic modulus improves and the CTE decreases. By setting the amount of the filler (D) to be 50 to 90% by mass in the solid content, a cured product with higher elasticity and lower CTE can be obtained.

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

[(A) Alkali-soluble resin having ethylenically unsaturated group]
The (A) alkali-soluble resin is a resin that contains at least one functional group of a phenolic hydroxyl group, a thiol group and a carboxyl group and an ethylenically unsaturated group, and is developable in an alkaline solution, and preferably phenol. Examples thereof include a photosensitive resin having two or more functional hydroxyl groups, a carboxyl group-containing photosensitive resin, a photosensitive resin having a phenolic hydroxyl group and a carboxyl group, and a photosensitive resin having two or more thiol groups. Here, "photosensitive" means having an ethylenically unsaturated group.
(A) The alkali-soluble resin more preferably has a carboxyl group, and a carboxyl group-containing photosensitive resin having an epoxy resin as a starting material, a carboxyl group-containing photosensitive resin having a phenol compound as a starting material, and a carboxyl having a copolymer structure The group-containing photosensitive resin and the photosensitive carboxyl group-containing resin having a urethane structure are more preferable. The ethylenically unsaturated group is preferably one derived from (meth)acrylic acid or a (meth)acrylic acid derivative.
Specific examples of the (A) alkali-soluble resin include, but are not limited to, the compounds (both oligomers and polymers) listed as (1) to (10) below.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate and isobutylene A carboxyl group having a copolymer structure, which is obtained by adding a compound having one epoxy group and one or more (meth)acryloyl group in the molecule, such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate. Contains photosensitive resin. The lower alkyl refers to an alkyl group having 1 to 5 carbon atoms.

(2-1) A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diisocyanate, a carboxyl group-containing dialcohol compound, and a diol compound, and further, one epoxy group and one or more (meth ) A carboxyl group-containing photosensitive resin having a urethane structure formed by adding a compound having an acryloyl group.
(2-2) having a urethane structure obtained by reacting a diisocyanate, a carboxyl group-containing dialcohol compound, a diol compound, and a compound having one hydroxyl group and one or more (meth)acryloyl group in the molecule Carboxyl group-containing photosensitive resin.
(2-3) a urethane structure obtained by reacting a diisocyanate, a carboxyl group-containing dialcohol compound, a diol compound, and a compound having one isocyanate group and one or more (meth)acryloyl group in the molecule Having a carboxyl group-containing photosensitive resin.
Here, examples of the diisocyanate include aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
Examples of the carboxyl group-containing dialcohol compound include dimethylolpropionic acid and dimethylolbutanoic acid.
Examples of the diol compound include polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, compounds having a phenolic hydroxyl group and an alcoholic hydroxyl group, and the like. To be
Examples of the compound having one hydroxyl group and one or more (meth)acryloyl group in the molecule include hydroxyalkyl (meth)acrylate.
Examples of the compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule include an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.

(3-1) Carboxyl group-containing urethane structure formed by polyaddition reaction of diisocyanate, (meth)acrylate of bifunctional epoxy resin or partial acid anhydride modified product thereof, carboxyl group-containing dialcohol compound and diol compound Photosensitive resin.
(3-2) A carboxyl having a urethane structure obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl group in the molecule to the carboxyl group-containing photosensitive resin of (3-2) Group-containing photosensitive resin.
(3-3) Diisocyanate, (meth)acrylate of bifunctional epoxy resin or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound, diol compound, one hydroxyl group and one or more hydroxyl groups in the molecule. A carboxyl group-containing photosensitive resin having a urethane structure, which is obtained by reacting with a compound having a (meth)acryloyl group.
(3-4) Diisocyanate, (meth)acrylate of bifunctional epoxy resin or partial acid anhydride modified product thereof, carboxyl group-containing dialcohol compound, diol compound, one isocyanate group and one or more in the molecule A carboxyl group-containing photosensitive resin having a urethane structure, which is obtained by reacting with the compound having a (meth)acryloyl group.

(4) A polyfunctional epoxy resin is reacted with an unsaturated monocarboxylic acid such as (meth)acrylic acid, and the hydroxyl group present in the side chain is dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride. Carboxyl group-containing photosensitive resin with added substances.

(5) A carboxyl group obtained by reacting an unsaturated group-containing monocarboxylic acid with a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl group. Contains photosensitive resin.

(6) 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 an unsaturated monoamine. A polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, etc. is reacted with the alcoholic hydroxyl group of the reaction product obtained by reacting with a carboxylic acid. A photosensitive resin containing a carboxyl group obtained by reacting with.

(7) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group, and further added with glycidyl (meth)acrylate and α-methylglycidyl (meth). ) A carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in a molecule such as acrylate.

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

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

(10) A compound having one epoxy group and one or more (meth)acryloyl group in the molecule as described above is added to the carboxyl group-containing photosensitive resin of (4) to (9) above. Carboxyl group-containing photosensitive resin.

The acid value of the (A) alkali-soluble resin is preferably in the range of 20 to 200 mgKOH/g, more preferably 40 to 150 mgKOH/g. When the acid value of the (A) alkali-soluble resin is 20 mgKOH/g or more, the adhesion of the coating film is good, and when the photocurable resin composition is used, alkali development is good. On the other hand, when the acid value is 200 mgKOH/g or less, the dissolution of the exposed area by the developer can be suppressed, so the line becomes unnecessarily thin, and in some cases, the exposed area and the unexposed area are not distinguished by dissolution in the developer. It is possible to draw a resist pattern satisfactorily by suppressing this.

As the alkali-soluble resin (A), the carboxyl group-containing photosensitive resins (4) to (10) are preferable, and the carboxyl group-containing photosensitive resins (8) and (9) are more preferable from the viewpoint of HAST resistance.

The weight average molecular weight of the (A) alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 50,000, more preferably 1,500 to 30,000. When the weight average molecular weight is 1,500 or more, tack-free performance is good, moisture resistance of the coating film after exposure is good, film loss during development can be suppressed, and deterioration of resolution can be suppressed. On the other hand, when the weight average molecular weight is 50,000 or less, the developability is good and the storage stability is also excellent.
The double bond equivalent of the (A) alkali-soluble resin is, for example, 500 to 3,500 eq. /G, which is 700 to 3,000 eq. from the viewpoint of resolution. /G is preferable.

As the alkali-soluble resin (A), one type may be used alone, or two or more types may be used in combination. Further, a conventionally known alkali-soluble resin having no ethylenically unsaturated group may be used in combination as long as the effect of the present invention is not impaired. The content of the alkali-soluble resin (A) in the entire composition is preferably 5 to 50% by mass, more preferably 10 to 50% by mass. When the amount is 5 to 50% by mass, the coating film strength is good, and the viscosity of the composition is appropriate, so that the coating property and the like can be improved.

[(B) At least two photopolymerization initiators that do not generate a base]
The (B) at least two photopolymerization initiators are not particularly limited as long as they do not generate a base. Examples of the photopolymerization initiator (B) that can be used as at least two photopolymerization initiators include, for example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide and 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, Bisacylphosphine oxide-based photopolymerization initiators such as bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE819 manufactured by BASF Japan Ltd.); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichloro. Benzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF Japan IRGACURE TPO) manufactured by K.K., etc., monoacylphosphine oxide photopolymerization initiator; 1-hydroxy-cyclohexyl phenyl ketone, 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 Hydroxyacetophenone-based photopolymerization initiators such as -methyl-1-phenylpropan-1-one; benzoin such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether -Based photopolymerization initiator; benzoin alkyl ether-based photopolymerization initiator; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloro Acetophenone-based photopolymerization initiators such as roacetophenone and 1-hydroxycyclohexyl phenyl ketone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, Anthraquinone-based photopolymerization initiators such as 2-aminoanthraquinone; Ketal-based photopolymerization initiators such as acetophenone dimethyl ketal and benzyl dimethyl ketal; ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-dimethylbenzoic acid Benzoate photopolymerization initiators such as acid ethyl ester; bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl ) Titanium-based photopolymerization initiators such as titanium and bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrr-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2 -Nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethyl thiuram disulfide and the like can be mentioned. The photopolymerization initiators may be used alone or in combination of two or more. Among them, (B1) an acylphosphine oxide-based photopolymerization initiator such as a monoacylphosphine oxide-based photopolymerization initiator and a bisacylphosphine oxide-based photopolymerization initiator, and (B2) a titanocene-based photopolymerization initiator are used in combination. Preferably.

The blending amount of (B) at least two photopolymerization initiators is preferably 5 to 30 parts by mass, and more preferably 10 to 20 parts by mass, relative to 100 parts by mass of the (A) alkali-soluble resin. ..

The compounding ratio of the (B1) acylphosphine oxide-based photopolymerization initiator and the (B2) titanocene-based photopolymerization initiator is preferably 10:1 to 200:1 on a mass basis.

In the composition of the present invention, it is preferable to use a sensitizer in combination with the photopolymerization initiator. Examples of the sensitizer include thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone. And benzophenone compounds such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone.
The compounding amount of the sensitizer is not particularly limited, but for example, the compounding ratio of the sensitizer and the photopolymerization initiator (B) is 1:2 to 1:100 on a mass part basis.

[(C) Thermosetting component]
The curable resin composition of the present invention contains (C) a thermosetting component. It can be expected that the heat resistance is improved by adding the thermosetting component. As the thermosetting component (C), one type may be used alone, or two or more types may be used in combination. As the thermosetting component (C), any known one can be used. For example, known thermosetting components such as melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimide, carbodiimide resins, etc. Can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio)ether groups) in the molecule.

The thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is a compound having a plurality of three-, four-, or five-membered cyclic (thio)ether groups in the molecule. A compound having an epoxy group, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.

As the polyfunctional epoxy compound, epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolac type epoxy resin; biphenol novolac type epoxy resin; bisphenol F Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidyl amine 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 novolac type epoxy resin; Tetraphenylolethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl xylenoyl ethane resin; Naphthalene group-containing epoxy resin; Dicyclopentadiene skeleton Examples of the epoxy resin include a glycidyl methacrylate copolymer epoxy resin, a cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin, an epoxy-modified polybutadiene rubber derivative, a CTBN-modified epoxy resin, and the like, but are not limited thereto. .. These epoxy resins may be used alone or in combination of two or more. Among these, novolac type epoxy resin, bisphenol type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolac type epoxy resin, naphthalene type epoxy resin or a mixture thereof is particularly preferable.

Examples of the polyfunctional oxetane compound include bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy)methyl]ether, 1,4-bis[(3- Methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methyl acrylate, (3-ethyl-3-) Oxetanyl)methyl acrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate, polyfunctional oxetanes such as oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly(p-hydroxystyrene), cardo type bisphenols, calixarenes, calixresorcinarenes, etherified products with resins having a hydroxyl group such as silsesquioxane, and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate may be used.

Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. Further, an episulfide resin in which an oxygen atom of an epoxy group of a novolac type epoxy resin is replaced with a sulfur atom by using the same synthetic method can be used. The amount of the thermosetting component having a plurality of cyclic (thio)ether groups in the molecule is such that the cyclic (thio)ether group is an alkali-soluble group 1 such as a carboxyl group or a phenolic hydroxyl group of the (A) alkali-soluble resin. It is preferably 0.6 to 2.5 equivalents, and more preferably 0.8 to 2.0 equivalents, relative to the equivalents.

Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds and methylolurea compounds.

As the isocyanate compound, a polyisocyanate compound can be blended. Examples of the polyisocyanate compound include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate and Aromatic polyisocyanates such as 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) and isophorone diisocyanate; bicyclo Examples thereof include alicyclic polyisocyanates such as heptane triisocyanate; and adducts, burettes and isocyanurates of the above-mentioned isocyanate compounds.

As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. Examples of the isocyanate compound capable of reacting with the isocyanate blocking agent include the above-mentioned polyisocyanate compound and the like. As the isocyanate blocking agent, for example, phenol blocking agent; lactam blocking agent; active methylene blocking agent; alcohol blocking agent; oxime blocking agent; mercaptan blocking agent; acid amide blocking agent; imide blocking agent; Amine blocking agents; imidazole blocking agents; imine blocking agents and the like.

The blending amount of the (C) thermosetting component is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. More preferably, it is 2 to 70 parts by mass.

[(D) Filler]
The curable resin composition of the present invention contains (D) a filler. By blending the (D) filler, the elastic modulus of the cured product can be improved and the CTE can be lowered. The filler (D) may be used alone or in combination of two or more. The filler (D) may be an organic filler or an inorganic filler, but an inorganic filler is preferable. Further, the (D) filler is preferably a surface-treated filler (surface-treated filler), and a cured product having high elasticity and low CTE can be obtained without impairing the resolution.
Here, the surface treatment of the (D) filler means a treatment for improving the compatibility with the (A) ethylenically unsaturated group-containing alkali-soluble resin or (C) thermosetting component. The surface treatment of the (D) filler is not particularly limited, and a surface treatment capable of introducing a curable reactive group onto the surface of the filler is preferable.

Examples of the inorganic filler include silica, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, titanium oxide, aluminum hydroxide, silicon nitride, aluminum nitride and the like. Among them, silica is preferable, and it suppresses the curing shrinkage of the cured product of the curable resin composition and improves the properties such as adhesion and hardness. Examples of silica include fused silica, spherical silica, amorphous silica, and crystalline silica.

The surface-treated filler is preferably a filler surface-treated with a coupling agent.
As the coupling agent, silane-based, titanate-based, aluminate-based and zircoaluminate-based coupling agents can be used. Of these, silane coupling agents are preferred. Examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amino. Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxy) Examples thereof include cyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. These can be used alone or in combination. These silane coupling agents are preferably immobilized on the surface of the filler in advance by adsorption or reaction. In the present invention, the coupling agent applied to the filler is not included in the organic compound (E) having an ethylenically unsaturated group.

The surface-treated filler preferably has a curable reactive group. The curable reactive group may be a thermosetting reactive group or a photocurable reactive group. As the thermosetting reactive group, hydroxyl group, carboxyl group, isocyanate group, amino group, imino group, epoxy group, oxetanyl group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group, etc. Are listed. Examples of the photocurable reactive group include a vinyl group, a styryl group, a methacryl group, and an acryl group. Above all, it is preferable to have an ethylenically unsaturated group such as a vinyl group, a styryl group, a methacryl group, and an acryl group, and a curable resin composition having more excellent resolution can be obtained. The surface-treated filler is more preferably silica having an ethylenically unsaturated group.

The average particle diameter of the (D) filler is preferably 5 μm or less. The compounding amount of the (D) filler is preferably 30 to 90% by mass based on the total solid content of the curable resin composition, and a cured product having higher elasticity and lower CTE can be obtained. More preferably, it is 50 to 90 mass %.

[(E) Organic compound having an ethylenically unsaturated group]
The curable resin composition of the present invention does not substantially contain (E) an organic compound having an ethylenically unsaturated group other than (A) an alkali-soluble resin having an ethylenically unsaturated group. Examples of the (E) organic compound having an ethylenically unsaturated group include acrylate compounds and the like that are blended with conventional curable resin compositions as photoreactive monomers.

Here, “substantially free from” means that it is not positively blended as a constituent, and it is not excluded that it is contained in a small amount within a range that does not impair the effects of the present invention. For example, it is 3 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin, and it is most preferable that the (E) organic compound having an ethylenically unsaturated group is not contained. .. The lower the content of the organic compound (E) having an ethylenically unsaturated group, the better the resolution.

(Colorant)
The curable resin composition of the present invention may contain a colorant. As the colorant, a commonly known colorant such as red, blue, green, yellow, white and black can be used, and any of pigments, dyes and pigments may be used. Specific examples include color index (C.I.; issued by The Society of Dyers and Colorists) numbers. However, from the viewpoint of reducing the environmental load and affecting the human body, it is preferable to use a halogen-free colorant.

Examples of the red colorant include monoazo type, diazo type, azo lake type, benzimidazolone type, perylene type, diketopyrrolopyrrole type, condensed azo type, anthraquinone type and quinacridone type. Blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based colorants, and pigment-based compounds include compounds classified as pigments. Similarly, the green colorants include metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based. Examples of the yellow colorant include monoazo type, disazo type, condensed azo type, benzimidazolone type, isoindolinone type and anthraquinone type. Examples of the white colorant include rutile type and anatase type titanium oxides. As the black colorant, titanium black-based, carbon black-based, graphite-based, iron oxide-based, anthraquinone-based, cobalt oxide-based, copper oxide-based, manganese-based, antimony oxide-based, nickel oxide-based, perylene-based, aniline-based Pigments, molybdenum sulfide, bismuth sulfide, etc. may be mentioned. In addition, colorants such as purple, orange and brown may be added for the purpose of adjusting the color tone.

The colorants may be used alone or in combination of two or more. The blending amount of the colorant is not particularly limited, but is preferably 10 parts by mass or less with respect to 100 parts by mass of the (A) alkali-soluble resin. It is more preferably 0.1 to 5 parts by mass.

(Organic solvent)
An organic solvent may be used in the curable resin composition of the present invention for the purpose of synthesizing (A) an alkali-soluble resin, preparing a composition, or adjusting the viscosity for applying to a substrate or a carrier film. it can. 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; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl. Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate , Esters such as 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, petroleum naphtha, hydrogenated petroleum naphtha , Petroleum-based solvents such as solvent naphtha. Such organic solvents may be used alone or in combination of two or more.

(Other optional ingredients)
If necessary, the curable resin composition of the present invention further comprises a photoinitiator aid, a cyanate compound, an elastomer, a mercapto compound, a thermosetting catalyst, a urethanization catalyst, a thixotropic agent, an adhesion promoter, and a block copolymer. , Chain transfer agents, polymerization inhibitors, copper damage inhibitors, antioxidants, rust inhibitors, UV absorbers, thickening agents such as finely divided silica, organic bentonite, montmorillonite, silicone-based, fluorine-based, polymer-based, etc. Defoaming agents and/or leveling agents, imidazole-based, thiazole-based, and triazole-based silane coupling agents, phosphinates, phosphoric acid ester derivatives, and flame retardants such as phosphorus compounds such as phosphazene compounds may be added. it can. As these, those known in the field of electronic materials can be used.

INDUSTRIAL APPLICABILITY The curable resin composition of the present invention is useful for forming a pattern layer as a permanent film of a printed wiring board such as a solder resist, a coverlay, and an interlayer insulating layer, and particularly useful for forming a solder resist. Moreover, since the curable resin composition of the present invention has excellent resolution, it can be suitably used for forming a pattern layer of an IC package which requires formation of a fine pattern. Further, since the cured product obtained from the curable resin composition of the present invention has a high elastic modulus and a low CTE, for example, an IC package substrate (printed wiring board used for an IC package having a small total thickness and insufficient rigidity). It can be preferably used for the formation of the pattern layer in (1).

The curable resin composition of the present invention may be in the form of a dry film provided with a carrier film (support) and a resin layer formed on the carrier film, the resin layer comprising the curable resin composition. At the time of forming a dry film, the curable resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to an appropriate value, and a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, a transfer roll coater. , A gravure coater, a spray coater or the like to apply a uniform thickness on the carrier film, and usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to obtain a film. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected within the range of 1 to 150 μm, preferably 10 to 60 μm.

A plastic film is used as the carrier film, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. The thickness of the carrier film is not particularly limited, but generally, it is appropriately selected within the range of 10 to 150 μm.

After depositing the curable resin composition of the present invention on a carrier film, a peelable cover film may be laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. preferable. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and the peeling force is more than the adhesive force between the membrane and the carrier film when peeling the cover film. It is sufficient if the adhesive force between the film and the cover film is smaller.

In the present invention, a resin layer may be formed by applying the curable resin composition of the present invention on the cover film and drying the resin layer, and a carrier film may be laminated on the surface of the resin layer. That is, as the film to which the curable resin composition of the present invention is applied when producing the dry film in the present invention, either a carrier film or a cover film may be used.

The printed wiring board of the present invention has a curable resin composition of the present invention or a cured product obtained from a resin layer of a dry film. As the method for producing a printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and a dip coating method on a substrate, After applying by a method such as a flow coating method, a roll coating method, a bar coater method, a screen printing method, or a curtain coating method, the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100°C. By doing so, a tack-free resin layer is formed. In the case of a dry film, the resin layer is formed on the substrate by sticking the resin layer on the substrate with a laminator or the like so that the resin layer contacts the substrate and then peeling off the carrier film.

Examples of the base material include a printed wiring board and a flexible printed wiring board on which circuits are previously formed of copper, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy. , Synthetic fiber epoxy, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. copper clad laminates for high frequency circuits, etc., all grades (FR-4 etc.) Plates and the like, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.

Volatile drying performed after applying the curable resin composition of the present invention, hot air circulation type drying furnace, IR furnace, hot plate, convection oven and the like (in the dryer using a heat source of air heating system by steam It is possible to use a method in which hot air is brought into countercurrent contact and a method in which hot air is blown onto the support from a nozzle).

After a resin layer is formed on the printed wiring board, it is selectively exposed to an active energy ray through a photomask on which a predetermined pattern is formed, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution). ) To form a cured product pattern. Further, the cured product is irradiated with an active energy ray and then heat-cured (for example, 100 to 220° C.), or after the heat-curing is irradiated with an active energy ray, or only the heat-curing is used for final finish curing (main curing) to bring about adhesion. A cured film having excellent properties such as properties and hardness is formed.

As the exposure machine used for the irradiation of active energy rays, a high-pressure mercury lamp lamp, an ultra-high-pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, or the like may be mounted, and an apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm may be used. Further, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer) can also be used. A lamp light source or a laser light source for a direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm. The exposure amount for image formation varies depending on the film thickness and the like, but it can be generally in the range of 10 to 1000 mJ/cm ² , and preferably 20 to 800 mJ/cm ² .

The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkaline solutions such as ammonia and amines can be used.

The present invention will be specifically described below with reference to Examples , Reference Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, "parts" and "%" are based on mass unless otherwise specified.

(Synthesis Example 1: Synthesis of alkali-soluble resin A-1 having ethylenically unsaturated group)
In an autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, and a stirring device, 119.4 parts of a novolac-type cresol resin (Showa Denko KK, Shonor CRG951, OH equivalent: 119.4), potassium hydroxide 1 0.19 parts and toluene 119.4 parts were introduced, the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 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. Thereafter, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with this reaction solution to neutralize potassium hydroxide, and the nonvolatile content was 62.1% and the hydroxyl value was 182.2 mgKOH/g (307. A propylene oxide reaction solution of a novolac type cresol resin having a concentration of 9 g/eq.) was obtained. This was an average of 1.08 mol of propylene oxide added per equivalent of the phenolic hydroxyl group.
The obtained propylene oxide reaction solution of novolac type cresol resin 293.0 parts, acrylic acid 43.2 parts, methanesulfonic acid 11.53 parts, methylhydroquinone 0.18 parts and toluene 252.9 parts were stirred with a stirrer and a temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, air was blown at a rate of 10 ml/min, and the reaction was carried out 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 was distilled out. Then, it was cooled to room temperature, the resulting reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the resulting 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 blowing tube, and air was supplied at a rate of 10 ml/min. Was blown in, and 60.8 parts of tetrahydrophthalic anhydride was gradually added while stirring, and the mixture was reacted at 95 to 101° C. for 6 hours, cooled, and taken out. In this way, a carboxyl group-containing photosensitive resin solution A-1 having a nonvolatile content of 65% and a solid acid value of 87.7 mgKOH/g was obtained.

(Synthesis Example 2: Synthesis of alkali-soluble resin A-2 having ethylenically unsaturated group)
Orthocresol novolac type epoxy resin (manufactured by DIC, EPICLON N-695, softening point 95° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (glycidyl group number (total aromatic ring number): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100° C. to be uniformly dissolved.
Then, 4.3 g of triphenylphosphine was charged, heated to 110° C. and reacted for 2 hours, 1.6 g of triphenylphosphine was further added, the temperature was raised to 120° C., and the reaction was further performed for 12 hours. Aromatic hydrocarbon (Solveso 150) 562 g and tetrahydrophthalic anhydride 684 g (4.5 mol) were charged into the obtained reaction liquid, and the reaction was carried out at 110° C. for 4 hours. Further, 142.0 g (1.0 mol) of glycidyl methacrylate was charged into the obtained reaction liquid, and the reaction was carried out at 115° C. for 4 hours to obtain a carboxyl group-containing photosensitive resin solution A-2. The solid content of the photosensitive resin solution A-2 thus obtained was 65%, and the acid value of the solid content was 87 mgKOH/g.

(Preparation of surface-treated filler (methacrylsilane-treated silica))
70 g of spherical silica (SFP-30M manufactured by Denka), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent are uniformly dispersed, A silica solvent dispersion D-1 was obtained.

(Preparation of surface-treated filler (aminosilane-treated silica))
70 g of spherical silica (SFP-30M manufactured by Denka), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd. as a silane coupling agent are uniformly dispersed, A silica solvent dispersion D-2 was obtained.

(Examples 1 to 7, 9, 10 , Reference Example 8 and Comparative Examples 1 to 3)
With various components shown in the following Table 1-3 were blended at proportions shown in Tables 1 to 3 (parts by weight), were preliminarily mixed using a stirrer and kneaded with bi Zumiru, to prepare a curable resin composition.

＊１：上記で合成したエチレン性不飽和基を有するアルカリ可溶性樹脂溶液Ａ−１
＊２：上記で合成したエチレン性不飽和基を有するアルカリ可溶性樹脂溶液Ａ−２
＊３：ＢＡＳＦジャパン社製イルガキュアＴＰＯ（２，４，６−トリメチルベンゾイル−ジフェニル−ホスフィンオキサイド）
＊４：岳陽市金茂泰科技有限公司社製ＪＭＴ７８４（チタノセン系光重合開始剤）
＊５：ＢＡＳＦジャパン社製イルガキュアＯＸＥ０２（エタノン，１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（ｏ−アセチルオキシム）
＊６：ＤＩＣ社製エピクロンＮ−７３０Ａ（フェノールノボラック型エポキシ樹脂）
＊７：三菱化学社製ｊＥＲ８２８（ビスフェノールＡ型エポキシ樹脂）
＊８：ＤＩＣ社製エピクロンＮ−８７０（ビスフェノールＡノボラック型エポキシ樹脂）
＊９：日本化薬社製ＮＣ−３０００Ｌ（ビフェニル／フェノールノボラック型エポキシ樹脂）
＊１０：上記で調整したメタクリルシランで表面処理されたシリカの溶剤分散品Ｄ−１
＊１１：上記で調整したアミノシランで表面処理されたシリカの溶剤分散品Ｄ−２
＊１２：ジペンタエリスリトールペンタアクリレート
＊１３：日本化薬社製カヤキュアＤＥＴＸ−Ｓ（２，４−ジエチルチオキサントン）
＊１４：青色顔料および黄色顔料

*1: Alkali-soluble resin solution A-1 having an ethylenically unsaturated group synthesized above
*2: Alkali-soluble resin solution A-2 having an ethylenically unsaturated group synthesized above
*3: Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF Japan Ltd.
*4: Yueyang Jinmo Tai Technology Co., Ltd. JMT784 (titanocene-based photopolymerization initiator)
*5: BASF Japan Irgacure OXE02 (ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime)
*6: DIC Corporation Epicron N-730A (phenol novolac type epoxy resin)
*7: Mitsubishi Chemical Corporation jER828 (bisphenol A type epoxy resin)
*8: DIC Corporation Epicron N-870 (bisphenol A novolac type epoxy resin)
*9: NC-3000L (biphenyl/phenol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.
*10: Solvent dispersion product D-1 of silica surface-treated with methacrylsilane prepared above
*11: Solvent dispersion product D-2 of silica surface-treated with aminosilane prepared above.
*12: Dipentaerythritol pentaacrylate *13: Nippon Kayaku Co., Ltd. Kayacure DETX-S (2,4-diethylthioxanthone)
*14: Blue pigment and yellow pigment

The curable resin compositions of Examples , Reference Examples and Comparative Examples shown in Tables 1 to 3 were evaluated by the methods shown below. The evaluation results are shown in Tables 1 to 3.

(Production of dry film)
The curable resin compositions of Examples 1 to 7, 9, 10 and Reference Example 8 and Comparative Examples 1 to 3 were applied on a 38 μm polyester film using an applicator, respectively, and dried at 80° C. for 20 minutes to prepare. ..

(Optimal exposure amount)
A single-sided printed wiring board on which a circuit having a copper thickness of 15 μm was formed was prepared and subjected to pretreatment using CZ8100 manufactured by MEC. Each of the dry films according to the examples , reference examples, and comparative examples prepared above was laminated on this substrate using a vacuum laminator so that the resin layer was in contact with the substrate, thereby forming a resin layer on the substrate. This substrate was exposed through a step tablet (Kodak No. 2) using an exposure device equipped with a high-pressure mercury short arc lamp, and developed (30° C., 0.2 MPa, 1% by mass Na ₂ CO ₃ aqueous solution) for 60 seconds. When the pattern of the step tablet remaining when the above procedure was carried out was 3 stages, the optimum exposure amount was determined.

(Characteristic test)
A single-sided printed wiring board on which a circuit having a copper thickness of 15 μm was formed was prepared and subjected to pretreatment using CZ8100 manufactured by MEC. Each of the dry films according to the example , the reference example and the comparative example produced above on this substrate, so that the resin layer is in contact with the substrate, by laminating using a vacuum laminator, the resin layer of the layer structure on the substrate Formed. This substrate was exposed to the solder resist pattern with the above-mentioned optimum exposure amount using an exposure device equipped with a high-pressure mercury short arc lamp, and then the carrier film was peeled off. Development was performed for 60 seconds under a condition of 0.2 MPa to obtain a patterned cured product. This substrate was irradiated with ultraviolet rays in a UV conveyor furnace under conditions of an integrated exposure amount of 1000 mJ/cm ² and then heated at 160° C. for 60 minutes to be cured. The characteristics of the obtained printed wiring board (evaluation substrate) were evaluated as follows.
(Resolution)
The pattern opening shape of the evaluation substrate was observed and evaluated. The judgment criteria are as follows. A: The diameter of the bottom of the opening is 40 μm, and the bottom can be confirmed.
○: The bottom diameter is 60 μm, and the bottom can be confirmed.
X: The diameter of the opening bottom is 60 μm, and the bottom cannot be confirmed.

(Storage elastic modulus)
GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on the shiny side (copper foil) of each of the dry films according to the examples , reference examples and comparative examples prepared above so that the resin layer was in contact with the substrate. A resin layer was formed on the copper foil by laminating with a vacuum laminator. An exposure device equipped with a high-pressure mercury short arc lamp was used for this, and the carrier film was peeled off after exposure with the above optimum exposure amount. This was irradiated with ultraviolet rays in a UV conveyor furnace under conditions of an integrated exposure amount of 1000 mJ/cm ² and then heated at 160° C. for 60 minutes to be cured. Then, the cured film was peeled off from the copper foil, and then a sample was cut into a measurement size (5 mm×50 mm, 40 μm size). The sample was subjected to DMS6100 (manufactured by Hitachi High-Tech Science Co., Ltd.) and the storage elastic modulus at 25° C. was measured at a frequency of 1 Hz.
⊚: Storage elastic modulus at 25° C. is 10 GPa or more.
Good: Storage elastic modulus at 25° C. is 7 GPa or more and less than 10 GPa.
X: Storage elastic modulus at 25° C. is less than 7 GPa.

(CTE)
GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.) was placed on the shiny side (copper foil) of each of the dry films according to the examples , reference examples and comparative examples prepared above so that the resin layer was in contact with the substrate. A resin layer was formed on the copper foil by laminating with a vacuum laminator. An exposure device equipped with a high-pressure mercury short arc lamp was used for this, and the carrier film was peeled off after exposure with the above optimum exposure amount. This was irradiated with ultraviolet rays in a UV conveyor furnace under conditions of an integrated exposure amount of 1000 mJ/cm ² and then heated at 160° C. for 60 minutes to be cured. After that, the cured film was peeled off from the copper foil, and a sample was cut into a measurement size (5 mm×50 mm size), and the sample was applied to TMA6100 manufactured by Seiko Instruments Inc. In the TMA measurement, the test load was 5 g, and the sample was heated from room temperature at a temperature rising rate of 10° C./min and continuously measured twice. The glass transition temperature (Tg) was defined as the intersection of two tangents having different linear expansion coefficients in the second time, and the coefficient of linear expansion (CTE(α1)) in the region of Tg or less was evaluated. The judgment criteria are as follows.
A: CTE at Tg temperature or lower is 20 ppm or lower.
◯: CTE at Tg temperature or less is 50 ppm or less.
Δ: CTE at Tg temperature or lower is 80 ppm or lower.
X: CTE at Tg temperature or lower exceeds 80 ppm.

From the results shown in the above table, it can be seen that the curable resin compositions of Examples 1 to 7, 9 and 10 of the present invention can give a cured product excellent in high resolution, high elasticity and low CTE. ..

Claims (6)

(A) an alkali-soluble resin having an ethylenically unsaturated group, (B) does not generate a base of at least two kinds of the photopolymerization initiator contains (C) a thermosetting component and (D) a filler,
A resin composition which does not substantially contain (E) an organic compound having an ethylenically unsaturated group other than the alkali-soluble resin having the above (A) ethylenically unsaturated group ,
The at least two photopolymerization initiators which do not generate the (B) base include (B1) an acylphosphine oxide-based photopolymerization initiator and (B2) a titanocene-based photopolymerization initiator in a weight ratio of 10:1 to 200: Included in the compounding ratio of 1,
The (D) filler contains a surface-treated filler surface-treated with a coupling agent having an ethylenically unsaturated group as a curable reactive group , wherein the curable resin composition (provided that the (D) filler is used. (E) is not included in the organic compound having an ethylenically unsaturated group) . Wherein (D) The curable resin composition according to claim 1 Symbol mounting comprises solids in 30-90 wt% of a filler curable resin composition. The surface treatment filler, the curable resin composition according to claim 1 or 2, wherein the surface-treated silica with the coupling agent having an ethylenically unsaturated group as the curable reactive group. Dry film characterized by having a resin layer obtained from the curable resin composition according to any one of claims 1-3. Curable resin composition or claim 4 cured product characterized by being obtained by curing the resin layer of the dry film according to according to any one of claims 1-3. A printed wiring board comprising the cured product according to claim 5 .