TW201742888A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

Provided are: a curable resin composition which is capable of providing a cured product that has excellent crack resistance and insulation reliability; a dry film which has a resin layer obtained from the composition; a cured product of the composition or the resin layer of the dry film; and a printed wiring board which comprises the cured product. A curable resin composition which is characterized by containing (A) a carboxyl group-containing resin and (B) an epoxy resin having a silsesquioxane skeleton; and the like.

Description

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, or a clad layer of a printed wiring board, for example, Patent Document 1 discloses a composition including a novolak type epoxy compound and A reaction product of a saturated monocarboxylic acid, an active energy ray-curable resin obtained by a reaction with a polybasic acid anhydride, a photopolymerization initiator, a photopolymerizable monomer, and an epoxy resin.

In recent years, with the rapid advancement of semiconductor components, electronic devices have become lighter, shorter, higher-performance, and more flexible. Following this trend, miniaturization and multi-needleization of semiconductor packages have been put into practical use. Specifically, an IC package called a BGA (Ball Grid Array) or a CSP (Chip Scale Package) is used instead of an IC package called QFP (Quad Flat Pack Package) or SOP (Small Outline Package). Further, in recent years, as a high-density IC package, there is also a practical FC-BGA (Flip chip. Ball grid array).

In a printed wiring board (also referred to as a package substrate) used in such an IC package, the SRO (Solder Resist Opening) pitch is narrowed and formed close to each other, and a short circuit or crosstalk noise between SROs is improved. . Further, since the solder resist formed between the SROs is thin and thin, cracks are likely to occur. Therefore, the permanent film such as the solder resist used for the package substrate is required to have high reliability over a long period of time, specifically, high crack resistance and high insulation reliability. In particular, with the increase in density of package substrates in the future, the requirements for reliability will be further improved.

In the past, as a photoresist composition for a package, as a composition for a photoresist which can be used, for example, Patent Document 2 discloses a photosensitive resin composition containing an organic polymer having an epoxy group-containing organic group. Oxygen, a phenol novolac having an acrylonitrile group, a polyfunctional monomer having a photofunctional group, and/or a diluent having a polyfunctional monomer having a photofunctional group and a thermal functional group, and a photopolymerization initiator.

Advanced technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 61-243869

Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-209183

However, the curable resin composition described in Patent Document 1 The material does not have a high degree of crack resistance and high insulation reliability. On the other hand, in the photosensitive resin composition described in Patent Document 2, since a phenol novolac having an acrylonitrile group is used, the curing temperature has to be increased, and the adhesion to the printed wiring board is low. Therefore, it becomes difficult to obtain crack resistance.

In other words, the permanent film such as the solder resist used in the conventional package substrate has room for improvement in crack resistance and insulation reliability.

In view of the above, an object of the present invention is to provide a curable resin composition of a cured product which is excellent in crack resistance and insulation reliability, a dry film of a resin layer obtained from the composition, a composition or a dry film. A cured product of the resin layer and a printed wiring board having the cured product.

In view of the above-described intensive investigation, the inventors of the present invention have found that the above problems can be solved by blending a carboxyl group-containing resin and an epoxy resin having a sesquisesquioxane skeleton, and the present invention has been completed. Further, by using a carboxyl group-containing resin, the carboxyl group-containing resin has a structure obtained by denaturation of a compound having two or more phenolic hydroxyl groups in one molecule to an alkylene oxide, which can further enhance Heat resistance and insulation reliability.

That is, the curable resin composition of the present invention contains (A) a carboxyl group-containing resin and (B) an epoxy resin having a sesquisesquioxane skeleton.

The curable resin composition of the present invention further contains (C) The surface treated inorganic filler is preferred.

In the curable resin composition of the present invention, the (A) carboxyl group-containing resin preferably has a structure represented by the following general formula (1).

(wherein R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group, and k represents a value of any of 0.3 to 10).

In the curable resin composition of the present invention, the (A) carboxyl group-containing resin preferably has a structure represented by the following general formula (2).

(wherein R ⁵ to R ⁷ each independently represent a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents a value of any of 0.3 to 10).

In the curable resin composition of the present invention, the epoxy resin having the sesquisesquioxane skeleton (B) has a structure represented by the following general formula (3).

(wherein R ⁸ to R ¹¹ are each independently a group having an SiO bond or an organic group, and at least one of R ⁸ to R ¹¹ is a group having an epoxy group).

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

The cured product of the present invention is characterized in that the curable resin composition or the resin layer of the dry film is cured.

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

According to the present invention, it is possible to provide a curable resin composition of a cured product which is excellent in crack resistance and insulation reliability, a dry film of the resin layer obtained by the composition, a resin layer of the composition or the dry film. A cured product and a printed wiring board having the cured product.

Form of implementing the invention

The curable resin composition of the present invention is characterized by comprising (A) a carboxyl group-containing resin and (B) an epoxy resin having a sesquisesquioxane skeleton.

Since the curable resin composition of the present invention contains a carboxyl group-containing resin and an epoxy resin having a sesquisesquioxane skeleton, the obtained cured product has a high glass transition temperature (Tg) and a linear expansion coefficient (CTEα1, α2). ) will be lower, and the elastic modulus (E) is higher at high temperatures. Therefore, at a high temperature, the fluidity of the cured product is suppressed, the stress is lowered, and the heat resistance is also excellent. In other words, it can be said that the cured product of the present invention has a high crosslinking density and hardly causes a change in physical properties at a high temperature.

In addition, the curable resin composition of the present invention contains an epoxy resin having a sesquisesquioxane skeleton, thereby suppressing warpage during curing and suppressing stress generated in the printed wiring board. Further, since the curable resin composition of the present invention contains a carboxyl group-containing resin and an epoxy resin having a sesquisesquioxane skeleton, the curability (reaction rate) at a low temperature is improved, and copper caused by high-temperature treatment can be suppressed. The oxidation of the circuit maintains the adhesion of the cured product to the printed wiring board.

Further, in the cured product of the present invention, since the modulus of elasticity at a high temperature is high, the crosslinking density is high and the water absorption rate is low. Although the detailed mechanism is not known, the cured product of the curable resin composition of the present invention is excellent in crack resistance and insulation reliability based on such heat resistance, low warpage, low-temperature curability, and low water absorption. Further, as will be described later, since the maximum value of Tan δ in the cured product at a temperature range of 25 to 300 ° C is small, stable crack resistance can be obtained. Further, the curable resin composition of the present invention can obtain a cured product excellent in resolution.

Each component of the curable resin composition of the present invention will be described below. Moreover, in the present specification, (meth) acrylate means acrylate, The general term for methyl acrylate and mixtures of these are the same for other similar performances.

[(A) carboxyl group-containing resin]

(A) The carboxyl group-containing resin is a component which is polymerized or crosslinked and hardened with the (B) epoxy resin, and contains a carboxyl group, and is soluble as an alkali. Further, from the viewpoint of photocurability or development resistance, it is preferred to have an ethylenically unsaturated group in the molecule in addition to the carboxyl group, but it is also possible to use only a carboxyl group-containing resin having no ethylenically unsaturated group. As the ethylenically unsaturated group, acrylic acid or methacrylic acid or a derivative derived therefrom is preferred. Among the carboxyl group-containing resins, a carboxyl group-containing resin having a copolymerization structure, a carboxyl group-containing resin having a urethane structure, a carboxyl group-containing resin using an epoxy resin as a starting material, and a phenol compound as a starting material are used. The carboxyl group-containing resin is preferred. Specific examples of the carboxyl group-containing resin include compounds (oligomer or polymer) as listed below.

(1) reacting a bifunctional or higher polyfunctional epoxy resin with (meth)acrylic acid to add a hydroxyl group having a side chain to a phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, or the like A carboxyl group-containing photosensitive resin of a 2-base acid anhydride. Here, the bifunctional or higher polyfunctional epoxy resin is preferably a solid.

(2) reacting a polyfunctional epoxy resin which oxidizes a hydroxyl group of a bifunctional epoxy resin with epichlorohydrin with (meth)acrylic acid, and adding a carboxyl group-containing sensitization of the generated hydroxyl group to a 2-base acid anhydride Resin. Here, the bifunctional epoxy resin is preferably a solid.

(3) An epoxy compound having two or more epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, and an unsaturated group containing (meth)acrylic acid or the like. The monocarboxylic acid reaction, and the alcoholic hydroxyl group of the obtained reaction product is reacted with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic anhydride. A carboxyl group-containing photosensitive resin.

(4) bisphenol A, bisphenol F, bisphenol S, novolac type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehyde, condensate of dihydroxynaphthalene and aldehyde, etc. 1 The reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with an alkylene oxide such as ethylene oxide or propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid to cause a reaction. A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(5) a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, and reacting with an unsaturated group-containing monocarboxylic acid to cause a reaction product A carboxyl group-containing photosensitive resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(6) a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a polycarbonate polyol, a polyether polyol, or a polyester polyol. a urethane obtained by a complex addition reaction of a diol compound such as a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide addition diol, or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group Resin The terminal is a urethane resin containing a terminal carboxyl group obtained by reacting it with an acid anhydride.

(7) Synthesis of a diisocyanate, a carboxyl group-containing diethanol compound such as dimethylolpropionic acid or dimethylol butyric acid, and a carboxyl group-containing urethane resin obtained by a complex addition reaction with a diol compound a carboxyl group-containing carbamate having a hydroxyl group and one or more (meth) acrylonitrile groups in a molecule such as a hydroxyalkyl (meth) acrylate and having a terminal (meth) acrylated Ester resin.

(8) Synthesis of a diisocyanate, a carboxyl group-containing diethanol compound, and a carboxyl group-containing urethane resin obtained by a complex addition reaction with a diol compound, wherein isophorone diisocyanate and pentaerythritol triacrylate are added A carboxyl group-containing urethane resin having a terminal (meth) acrylated compound having one isocyanate group and one or more (meth) acrylonitrile groups in the molecule, such as a molar reactant.

(9) Copolymerization of an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene The obtained carboxyl group-containing photosensitive resin.

(10) A carboxyl group-containing polyester obtained by reacting a polyfunctional tetracyclic ether resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form a first-stage hydroxyl group to be added to a 2-base acid anhydride Resin.

(11) A carboxyl group-containing photosensitive resin having a compound having a cyclic ether group and a (meth) acrylonitrile group in one molecule, which is a carboxyl group-containing resin of any one of the above (1) to (10).

The carboxyl group-containing resin is preferably a carboxyl group-containing resin of the above (1), (4), (5), and (9), and is considered to have an improved heat resistance (glass transition temperature) of the cured product. The carboxyl group-containing resin of 1), (4), and (5) is preferred. Among them, the carboxyl group-containing resin of the above (4) and (5) is more preferable from the viewpoint of insulation reliability. Further, as the above (4) and (5), a carboxyl group-containing resin having a structure represented by the following general formula (1) can be suitably used.

(wherein R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group, and k represents a value of any of 0.3 to 10).

The alkyl group obtained as R ¹ to R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms.

Further, as described in the above (4) and (5), a carboxyl group-containing resin having a structure represented by the following general formula (2) can be suitably used.

(wherein R ⁵ to R ⁷ each independently represent a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents a value of any of 0.3 to 10).

As R ⁵ ~ R ⁷ obtained from an alkyl group, preferably an alkyl group of 1 to 20 carbon atoms.

The acid anhydride residue obtained as Z is an acid anhydride residue derived from a carboxylic acid anhydride shown below, and examples thereof include tetrahydrophthalic anhydride, maleic anhydride, succinic anhydride, trimellitic anhydride, and pyromellitic anhydride. Anhydride residue.

The carboxyl group-containing resin having the structure represented by the above general formula (1) and the structure represented by the above general formula (2) is exemplified by two of the molecules of the above (4) or (5). A carboxyl group-containing resin of a reaction product of the above phenolic hydroxyl group with a alkylene oxide or a cyclic carbonate compound, a reaction with a carboxylic acid having an ethylenically unsaturated group, and a polybasic acid anhydride. Further, the reaction product of a compound having two or more phenolic hydroxyl groups in one molecule and a alkylene oxide or a cyclic carbonate compound is not only a carboxylic acid having an ethylenically unsaturated group, but also After reacting with at least one of a saturated aliphatic monocarboxylic acid and an aromatic monocarboxylic acid, and reacting it with a carboxylic acid having an ethylenically unsaturated group and a polybasic acid anhydride.

Examples of the compound having two or more phenolic hydroxyl groups in one molecule include catechol, resorcin, hydroquinone, dihydroxytoluene, naphthalenediol, t-butylcatechol, and t. -butyl hydroquinone, gallic phenol, phloroglucinol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl Ether, phenolphthalein, novolac type phenol resin, condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, poly-p-hydroxystyrene, 1-naphthol or 2-naphthol and aldehydes (ie, naphthol novolak resin), 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 2,3-, 2,6-, 2,7- a condensate of dihydroxynaphthalene and an aldehyde, a condensate of a mononaphthol with the above dihydroxynaphthalene and an aldehyde, a condensate of a mono- or dihydroxynaphthalene with a decanediol, or a mono- or dihydroxynaphthalene and a diene compound Adults, etc., but are not limited to these. These compounds having a phenolic hydroxyl group can be used singly or in combination of two or more kinds.

In the above compound having a phenolic hydroxyl group, a functional group containing a halogen atom, oxygen, nitrogen, sulfur, or the like, which is bonded to a phenol ring or a hydrocarbon skeleton of a phenol ring, has, for example, a halogen group, an ether group, or an ester group. A heteroaromatic group such as a carbonyl group, a hydroxyl group, an aldehyde group, an amine group, a decylamino group, a nitrile group, a nitro group, a thiol group, a thioether group, another pyridyl group or an imidazolyl group.

Among these compounds having a phenolic hydroxyl group, a compound having three or more phenolic hydroxyl groups in one molecule is preferred, and a novolac type phenol resin, a phenol, and an aromatic aldehyde having a phenolic hydroxyl group are preferred. Condensate.

An alkylene oxide relative to the above compound having a phenolic hydroxyl group The addition ratio is preferably 1 to 10.0 mol per phenolic hydroxyl group per phenolic hydroxyl group. When it is 0.3 mol or more, the photocurability of the obtained photosensitive carboxyl group-containing resin is good. Moreover, when it is 10.0 mol or less, photocurability and thermosetting property are favorable.

The addition reaction of the alkylene oxide is preferably carried out at a normal temperature to 250 ° C with respect to the above compound having a phenolic hydroxyl group. As the reaction solvent, benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, and the like are suitably used. Isopropyl ether and the like. These organic solvents can be used singly or in combination of two or more kinds.

As the reaction catalyst, an alkali metal compound such as potassium carbonate, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide or barium hydroxide, a tertiary amine such as triethylamine or the like, 2-ethyl-4-methyl is preferably used. Imidazole compound such as imidazole, tri compound such as triphenylphosphine, tetramethylammonium chloride, tetrabutylammonium bromide, trimethylbenzylammonium halide, ammonium tetramethylbenzoate, tetramethyl hydroxide a fourth-order base salt compound of ammonium, tetraethylammonium hydroxide or tetramethylphosphonium hydroxide, lithium, chromium, zirconium, potassium, naphthenic acid, lauric acid, stearic acid, oleic acid or octanoic acid, A metal such as sodium or the like. These catalysts can be used alone or in combination of two or more types.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,3-propylene oxide, tetrahydrofuran, and tetrahydropyran. As the cyclic carbonate compound, a conventionally known carbonate compound can be used, and examples thereof include ethylene carbonate, propylene carbonate, butyl carbonate, and 2,3-carbonate propyl acrylate, and preferably 5 Ethylene carbonate, propylene carbonate It is preferred in terms of reactivity. These alkylene oxides and cyclic carbonate compounds can be used alone or in combination of two or more.

The reaction product obtained by reacting the compound having a phenolic hydroxyl group with an alkylene oxide or a cyclic carbonate compound is reacted with a monocarboxylic acid containing an unsaturated group to obtain a reaction product, but in the esterification reaction at this time The reaction temperature is preferably from 50 to 120 ° C, and the reaction can be carried out under reduced pressure, at normal pressure or under pressure. In the esterification reaction, the unsaturated group-containing monocarboxylic acid is preferably used in an amount of 300 to 800 g/eq., based on the double bond equivalent of the photosensitive carboxyl group-containing resin.

As the reaction solvent, benzene, toluene, xylene, tetramethylbenzene, n-hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, octane, methyl isobutyl ketone, or the like is suitably used. Diisopropyl ether and the like. These organic solvents can be used singly or in combination of two or more kinds.

As the esterification catalyst, sulfuric acid, hydrochloric acid, citric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, a cation exchange resin or the like is suitably used. The esterification reaction is preferably carried out in the presence of a polymerization inhibitor, and as the polymerization preventive agent, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, gallic phenol or the like is suitably used.

Representative examples of the unsaturated group-containing monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-mercaptoacrylic acid. Among these, acrylic acid and methacrylic acid are particularly preferred. These unsaturated group-containing monocarboxylic acids can be used singly or in combination of two or more.

The reaction product of the foregoing and the monocarboxylic acid containing an unsaturated group The reaction product is reacted with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin (photosensitive prepolymer). However, in this reaction, the polybasic acid anhydride is used in an amount such that the generated carboxyl group-containing photosensitive resin is acid. The price is preferably from 20 to 200 mgKOH/g, more preferably from 50 to 120 mgKOH/g, as the addition amount. The reaction is carried out in the presence or absence of an organic solvent described later, and in the presence of a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, gallic phenol, etc., usually at about 50 to 150. Perform at °C. At this time, if necessary, a tertiary amine such as triethylamine or a tertiary ammonium salt such as triethylbenzylammonium chloride or an imidazole compound such as 2-ethyl-4-methylimidazole or triphenyl may be added. A phosphorus compound such as a phosphine, a naphthenic acid, lauric acid, stearic acid, a metal salt of an organic acid such as lithium, chromium, zirconium, potassium or sodium of oleic acid or octanoic acid is used as a catalyst. These catalysts can be used alone or in combination of two or more types.

Examples of the above-mentioned polybasic acid anhydride include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methylenetetrahydroortylene. An alicyclic dibasic anhydride such as dicarboxylic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride or tetrabromophthalic anhydride; succinic anhydride An aliphatic or aromatic dibasic or tribasic anhydride of maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, phthalic anhydride, trimellitic anhydride, or the like, or Pyromellitic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, etc. One or two or more of these may be used as the aliphatic or aromatic tetrabasic acid dianhydride. Among these, alicyclic dibasic acid anhydrides are particularly preferred.

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

(A) The blending amount of the carboxyl group-containing resin is preferably from 15 to 60% by mass, and preferably from 20 to 60% by mass based on the total amount of the curable resin composition from which the solvent is removed. When the amount is 15% by mass or more, preferably 20% by mass or more, the coating film strength can be improved. Further, by being 60% by mass or less, the viscosity is appropriate and the workability is improved. More preferably, it is 30 to 50% by mass. (A) The carboxyl group-containing resin can be used singly or in combination of two or more.

[(B) Epoxy resin having a sesquisesquioxane skeleton]

(B) an epoxy resin having a sesquisesquioxane skeleton (hereinafter referred to as "(B) epoxy resin"), as long as it is a sesquisesquioxane, that is, obtained by hydrolyzing a trifunctional decane The network type polymer or polyhedral polymer having a structure of (RSiO _1.5 ) _n and a compound having a group containing an epoxy group are not particularly limited. Each of the oxime sesquioxanes is bonded to an average of 1.5 oxygen atoms and one hydrocarbon group. Here, the epoxy resin (B) is preferably an epoxy resin which does not contain a halogen atom.

(B) As the epoxy resin, a semiquinoxane skeleton represented by the following general formula (3) is preferred.

(wherein R ⁸ to R ¹¹ are each independently a group having an SiO bond or an organic group, and at least one of R ⁸ to R ¹¹ is a group having an epoxy group), wherein the organic group means a carbon atom base.

The structure of the above-mentioned sesquisestamer is not particularly limited, and a sesquioxanes of a known and conventional structure such as a random structure, a trapezoidal structure, a completely cage structure, or an incomplete cage structure can be used.

The group having an SiO bond obtained by R ⁸ to R ¹¹ is not particularly limited, and examples thereof include a group having an SiO bond and an aliphatic skeleton, a group having an SiO bond and an aromatic skeleton, and having an SiO bond and The base of the hetero atom or the like is preferably within the range of the epoxy equivalent described below.

The organic group obtained by R ⁸ to R ¹¹ is not particularly limited, and examples thereof include an aliphatic group such as a methyl group, an aromatic group such as a phenyl group, and an organic group having a hetero atom. The organic group having 1 to 30 carbon atoms is preferred, and it is preferably within the range of the epoxy equivalent described below.

At least one of R ⁸ to R ¹¹ is a group having an epoxy group, and the group having an epoxy group is not particularly limited as long as it is a group having an SiO bond or an organic group having an epoxy group.

(B) The epoxy equivalent of the epoxy resin is from 100 to 400 g/eq. More preferably, it is from 150 to 250 g/eq. More preferably. When it is above 100g/eq., save the security Qualitatively good. When it is 400 g/eq. or less, the CTE (α1, α2) of the cured product can be lowered.

(B) The blending amount of the epoxy resin is, for example, 1 to 100 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 80 parts by mass, per 100 parts by mass of the (A) carboxyl group-containing resin. It is more preferably 10 to 60 parts by mass, particularly preferably 20 to 60 parts by mass, and most preferably 25 to 60 parts by mass. (B) When the blending amount of the epoxy resin is 1 part by mass or more, the crack resistance and the insulation reliability are further improved, and when it is 100 parts by mass or less, the storage stability is improved.

((C) surface treated inorganic filler)

The curable resin composition of the present invention preferably contains an inorganic filler, and the inorganic filler is preferably (C) a surface-treated inorganic filler (hereinafter simply referred to as "(C) inorganic filler"). By including (C) an inorganic filler, the crack resistance of the cured product is further enhanced. Here, the surface treatment of the (C) inorganic filler means a treatment for improving the compatibility with the (A) carboxyl group-containing resin or (B) epoxy resin. (C) The surface treatment of the inorganic filler is not particularly limited, and a surface treatment capable of introducing a curable reactive group on the surface of the inorganic filler is preferred.

The inorganic filler is not particularly limited, and conventionally known fillers such as cerium oxide, crystalline cerium oxide, nunloy bauxite, aluminum hydroxide, glass powder, mica, clay, magnesium carbonate, and calcium carbonate can be used. , natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, asbestos, aluminum silicate, antimony Inorganic fillers such as calcium acid and zinc. Among them, cerium oxide is preferred, the surface area is small, and the stress is dispersed throughout the entire layer. Therefore, it is difficult to be a starting point of the crack, and since the resolution is excellent, spherical cerium oxide is more preferable.

(C) The inorganic filler is preferably a curable reactive group having at least one of (A) a carboxyl group-containing resin and (B) an epoxy resin reacted on the surface. The curable reactive group may also be a thermosetting reactive group or a photocurable reactive group. Examples of the thermosetting reactive group include a hydroxyl group, a carboxyl group, an isocyanate group, an amine group, an imido group, an epoxy group, an oxypropylene group, a decyl group, a methoxymethyl group, a methoxyethyl group, and an ethoxy group. Methyl, ethoxyethyl, oxazoline or the like. Examples of the photocurable reactive group include a vinyl group, a styryl group, a methacrylic group, and an acrylic group. Among them, the photocurable reactive group is preferably a methacrylic group, an acrylic group or a vinyl group, and as the thermosetting reactive group, an epoxy group is preferred. Further, the (C) inorganic filler may have two or more kinds of hardening reactive groups. As the (C) inorganic filler, surface-treated cerium oxide is preferred. The glass transition temperature can be increased by including the surface treated two gasified ruthenium.

The method of introducing the curable reactive group on the surface of the (C) inorganic filler is not particularly limited, and it may be introduced by a conventionally known method, and a surface treating agent having a curable reactive group, for example, having a curable reactive group A mixture or the like can be used to treat the surface of the inorganic filler.

As the surface treatment of the (C) inorganic filler, the surface treatment of the coupling agent is preferred. As the coupling agent, a decane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Among them, a decane coupling agent is preferred.

As the decane coupling agent, a decane coupling agent capable of introducing a curing reactive group into the (C) inorganic filler is preferred. Examples of the decane coupling agent capable of introducing a thermosetting reactive group include a decane coupling agent having an epoxy group, a decane coupling agent having an amine group, a decane coupling agent having a mercapto group, and a decane coupling agent having an isocyanate group, among which An epoxy group decane coupling agent is further preferred. The decane coupling agent capable of introducing a photo-curing reactive group is preferably a decane coupling agent having a vinyl group, a decane coupling agent having a styryl group, a decane coupling agent having a methacryl group, and a decane coupling agent having an acryl group. Among them, a decane coupling agent having a methacryl group is more preferable.

Further, as the (C) inorganic filler having no curable reactive group, for example, an inorganic filler surface-treated with alumina may be mentioned.

(C) The inorganic filler may be blended in the surface of the curable resin composition of the present invention in a surface-treated state, or may be blended with an untreated inorganic filler and a surface treating agent, respectively, and then inorganic in the composition. The filler is surface-treated, but it is preferred to incorporate an inorganic filler previously surface-treated. By blending the inorganic filler previously surface-treated, it is possible to prevent a decrease in crack resistance or the like due to the surface treatment agent which is not consumed by the surface treatment remaining at the time of blending. In the pre-surface treatment, it is preferred to blend the solvent or the resin in a minute to prepare a preliminary dispersion in which the (C) inorganic filler is preliminarily dispersed, and the surface-treated inorganic filler is preliminarily dispersed in a solvent, and the preliminary dispersion is blended in the composition. Further, it is more preferable to incorporate the preliminary dispersion into the composition after sufficiently pretreating the surface of the untreated inorganic filler in the solvent.

In the curable resin composition of the present invention, the average particle diameter of the inorganic filler is preferably 2 μm or less from the viewpoint of further excellent crack resistance. More preferably, it is 1 micrometer or less. Further, in the present specification, the average particle diameter means a value of D50 measured by a Microtrac particle size analyzer manufactured by Nikkiso Co., Ltd.

The blending amount of the inorganic filler is preferably from 20 to 80% by mass based on the total amount of the solid content of the curable resin composition, more preferably from 30 to 80% by mass, still more preferably from 35 to 80% by mass.

The curable resin composition of the present invention may also be used in combination with (C) an inorganic filler and an inorganic filler which is not surface-treated. In this case, the total amount of the (C) inorganic filler in the (C) inorganic filler and the inorganic filler not subjected to the surface treatment is preferably 30% by mass or more, more preferably 50% by mass or more, and still more preferably 70% by mass or more. good. Further, the inorganic filler which is not surface-treated is preferably spherical cerium oxide.

(at least one of a photopolymerization initiator and a photobase generator)

When the curable resin composition of the present invention is photocurable, at least one of a photopolymerization initiator and a photobase generator is preferably used. As the photopolymerization initiator, any photopolymerization initiator or photoradical generator can be used as long as it is a known photopolymerization initiator.

As the photopolymerization initiator, for example, bis-(2,6-dichlorobenzylidene) phenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-2,5-dimethyl group is mentioned. Phenylphosphine oxide, bis-(2,6-dichlorobenzylidene)-4-propyl phenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-1-naphthylphosphine oxide, double -(2,6- Dimethoxybenzhydryl) phenylphosphine oxide, bis-(2,6-dimethoxybenzhydryl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-di Double of methoxybenzhydryl)-2,5-dimethyloxyphenylphosphine, bis-(2,4,6-trimethylbenzylidene)-oxyphenylphosphine (IRGACURE 819, manufactured by BASF JAPAN) Thiol phosphine oxide; 2,6-dimethoxybenzhydryl phenylphosphine oxide, 2,6-dichlorobenzhydryl phenylphosphine oxide, 2,4,6-trimethylbenzylidene Methyl phenyl phenylphosphonate, 2-benzoic acid methyl phenylphosphine oxide, isopropyl trimethylethyl phenyl phenylphosphonate, 2,4,6-trimethyl benzhydryl phenylphosphine diphenyl phosphine Monothiol phosphines such as IRGACURETPO (BASF JAPAN); 1-hydroxy-cyclohexyl benzophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl Base-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propane Hydroxyacetophenones such as 1-ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin Benzoin, benzoin n-butyl ether, etc.; benzoin alkyl ether; benzophenone, p- Dibenzophenone, Michler's ketone, methyl benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylamine benzophenone Ketones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichlorobenzene Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamine 1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamine)-2-[(4-methylphenyl)methyl)-1-[4-(4- Acetophenones such as phenyl]-1-butanone, N,N-dimethylamine acetophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthene Ketone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthene Thioxanone such as ketone, 2-chlorothioxanthone or 2,4-diisopropylthioxanthone; leek, leeks, 2-methyl leeks, 2-ethyl leeks, 2- Tert-butyl leeks, 1-chloro leeks, 2-pentyl leeks, 2-amine leeks, etc.; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. a ketal; a benzoic acid ester of dimethyl 4-amino benzoate, ethyl 2-(dimethylamine)benzoate, ethyl p-dimethylbenzoate; 1,2- Octanedione, 1-[4-(phenylsulfanyl)-,2-(O-benzylidenehydrazide)], ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl) Anthracene ester of -9H-carbazolyl-3-yl]-, 1-(O-acetamidine); bis(η5-2,4-cyclopentadien-1-yl)-bis(2) ,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrole- Titanium quinones such as 1-yl)ethyl)phenyl]titanium; phenyl sulfonate 2-nitrate, butyl acetoin, anise ate ether, azobisisobutyronitrile, tetramethylammonium thioformate Base. The photopolymerization initiator may be used singly or in combination of two or more. Among them, mono-decylphosphine oxides and oxime esters are preferably 2,4,6-trimethylbenzimidyl phenylphosphine oxide, ethyl ketone, 1-[9-ethyl-6-(2) Further, benzoic acid methyl)-9H-carbazolyl-3-yl]-, 1-(O-acetyl) is further preferred.

The blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. When it is 0.5 part by mass or more, the surface hardenability is preferably good, and when it is 20 parts by mass or less, blooming is hard to occur, and good resolution is obtained.

When a photobase generating agent is irradiated with light such as ultraviolet light or visible light, the molecular structure changes or a molecule is cleaved to form a compound of one or more kinds of basic substances capable of functioning as a catalyst for a thermosetting reaction. Examples of the base material include a secondary amine and a tertiary amine.

Examples of the photobase generating agent include an α-aminoacetophenone compound, an oxime ester compound, an N-methylated aromatic amine compound, an N-deuterated aromatic amine compound, and a nitrobenzyl carbamate. a compound, an alkoxybenzyl carbamate compound or the like. Among them, an oxime ester compound and an α-aminoacetophenone compound are preferred, and an oxime ester compound is more preferably an ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl)-9H. Further, oxazolyl-3-yl]-, 1-(O-acetamidine) is preferred. The α-aminoacetophenone compound is particularly preferably one having two or more nitrogen atoms. The photobase generating agent may be used alone or in combination of two or more.

Other examples of the photobase generating agent include a grade 4 ammonium salt.

As another photobase generator, WPBG-018 (trade name: 9-anthrylmethyl N, N'-diethylcarbamate), WPBG-027 (trade name: (E)-1-[3-(2-hydroxyphenyl)) can be used. -2-propenoyl]piperidine), WPBG-082 (trade name: guanidinium2-(3-benzoylphenyl)propionate), WPBG-140 (trade name: 1-(anthraquinon-2-yl)ethyl imidazolecarboxylate).

Further, a substance of a part of the photopolymerization initiator may also function as a photobase generator. The photopolymerization initiator which is a function of a photobase generator is preferably an oxime ester photopolymerization initiator and an α-aminoacetophenone photopolymerization initiator.

The amount of the photobase generator blended relative to (A) carboxyl group The resin is preferably used in an amount of 0.1 to 20 parts by mass. When it is 0.1 part by mass or more, the surface hardenability is preferably good, and when it is 20 parts by mass or less, blooming is difficult to occur, and good resolution can be obtained.

(a compound having an ethylenically unsaturated group)

When the curable resin composition of the present invention is photocurable, a compound having one or more ethylenically unsaturated groups in the molecule is preferably used. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable ethylene monomer, or the like of a photosensitive monomer which is conventionally used can be used. Further, the compound having an ethylenically unsaturated group as described herein does not contain (A) a carboxyl group-containing resin having an ethylenically unsaturated group and (C) a surface-treated inorganic filler.

Examples of the photopolymerizable oligomer include an unsaturated polyester oligomer and a (meth)acrylate oligomer. Examples of the (meth) acrylate-based oligomer include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, and bisphenol epoxy (meth) acrylate. Epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (methyl) Acrylate, polybutadiene denatured (meth) acrylate, and the like.

Examples of the photopolymerizable ethylene monomer include known styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl acetate, vinyl butyrate, and vinyl benzoate; Vinyl esters; ethylene isobutyl ether, ethylene-n-butyl ether, ethylene-t-butyl ether, ethylene - N-dipentyl ether, ethylene iso-dipentyl ether, ethylene-n-octadecyl ether, ethylene cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, etc. Vinyl ethers; acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl propylene amide, N-ethoxy (meth) acrylamide such as methacrylamide or N-butoxymethyl acrylamide; triallyl isocyanurate, diallyl phthalate, isophthalic acid Allyl ester compound such as allyl ester; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfural (meth) acrylate, isobornyl (meth) acrylate Esters of (meth)acrylic acid such as ester, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate a hydroxyalkyl (meth) acrylate such as an ester or pentaerythritol tri(meth) acrylate; an alkoxy group such as methoxyethyl (meth) acrylate or ethoxyethyl (meth) acrylate; Alkyl glycol (Meth)acrylates; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6- Alkylene glycol polyols such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (meth) acrylate; diethylene glycol di(meth) acrylate, triethylene glycol di(meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane a polyoxyalkylene glycol poly(meth)acrylate such as a tris(meth)acrylate; a poly(ethylene) hydroxypivalate dipentaethylene glycol di(meth)acrylate or the like Acrylates; isocyanate type poly(meth)acrylates such as [(meth)acryloxyethyl)isocyanate. These combinations of the required characteristics can be used alone or in combination of two or more.

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

(thermosetting catalyst)

The curable resin composition of the present invention preferably contains a thermosetting catalyst. As such a thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- An imidazole derivative such as cyanoethyl-2-phenylimidazole or 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(Dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl An amine compound such as a base amine, a hydrazine compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like. Further, it is also possible to use guanamine, acetamide, benzoguanamine, melamine, 2,4-diamine-6-methacrylic acid oxyethyl-S-triazabenzene, 2-ethylene-2,4. -diamine-S-triazabenzene, 2-ethylene-4,6-diamine-S-triazabenzene. Iso-cyanuric acid adduct, 2,4-diamine-6-methacrylic acid oxyethyl-S-triazabenzene. The S-triazabenzene derivative such as an isocyanuric acid addition product is preferably used in combination with a thermosetting catalyst which can also function as a tackifier.

The blending amount of the heat-hardening catalyst is, for example, 0.05 to 80 parts by mass, preferably 0.05 to 50 parts by mass, more preferably 0.05 to 40 parts by mass, more preferably 100 parts by mass based on the (B) epoxy resin. It is 0.1 to 30 parts by mass.

(hardener)

The curable resin composition of the present invention can contain a curing agent. Examples of the curing agent include a phenol resin, a polycarboxylic acid, an acid anhydride thereof, a cyanate resin, an active ester resin, a maleimide compound, an alicyclic olefin polymer, and the like. The curing agent can be used singly or in combination of two or more.

(B) a functional group capable of undergoing a thermosetting reaction such as an epoxy group in a thermosetting resin such as an epoxy resin, and a hardening reaction with a functional group thereof, in the thermosetting resin such as an epoxy resin. The ratio of the functional groups in the agent is a functional group of the hardener/functional group capable of performing a thermosetting reaction (equivalent ratio) = 0.2 to 3. By setting it in the above range, the balance between preservation stability and hardenability is excellent.

(Colorant)

A coloring agent may also be contained in the curable resin composition of the present invention. As the coloring agent, a known coloring agent such as red, blue, green, yellow, black or white can be used, and any of a pigment, a dye, and a coloring matter can be used. However, it is preferable to contain no halogen from the viewpoint of a reduction in environmental load and influence on the human body.

The amount of the coloring agent to be added is not particularly limited, but is preferably 10 parts by mass or less based on 100 parts by mass of the (A) carboxyl group-containing resin. It is particularly preferable to use a ratio of 0.1 to 7 parts by mass.

(Organic solvents)

The curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when applied to a substrate or a carrier film. As the organic solvent, ketones such as methyl ethyl ketone or cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; 赛路苏, methyl 赛路苏, butyl 赛路苏, 卡必Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, etc. Glycol ethers; ethyl acetate, butyl acetate, butyl lactate, 赛苏苏 acetate, butyl succinate acetate, carbitol acetate, butyl carbitol acetate, propylene glycol An ester of monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate or the like; an aliphatic hydrocarbon such as octane or decane; a petroleum solvent such as petroleum ether, petroleum brain or solvent petroleum brain And other known organic solvents. These organic solvents can be used singly or in combination of two or more kinds.

(other optional ingredients)

Further, in the curable resin composition of the present invention, other additives conventionally used in the field of electronic materials may be blended. As other additives, there are mentioned thermal polymerization inhibitors, ultraviolet absorbers, decane coupling agents, plasticizers, flame retardants, antistatic agents, aging inhibitors, and antibacterial agents. Antifungal agent, antifoaming agent, leveling agent, tackifier, adhesion imparting agent, thixotropic agent, photoinitiator, sensitizer, thermoplastic resin, organic filler, A release 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 the epoxy resin (B) within a range not impairing the effects of the present invention. The thermosetting resin may be any resin which is cured by heating and which exhibits electrical insulating properties, and examples thereof include an epoxy compound other than the epoxy resin, a tetracyclic ether compound, a melamine resin, a fluorene resin, and the like. These can also be used together.

The thermosetting resin other than the epoxy resin (B) is preferably a compound having a plurality of cyclic (thio)ether groups in the molecule. a compound having a plurality of cyclic (thio)ether groups in the above molecule, which is a compound having a cyclic (thio)ether group having a plurality of 3, 4 or 5 membered rings in the molecule, and for example, a compound having a plurality of epoxy groups in the molecule That is, a polyfunctional epoxy compound, a compound having a complex propylene oxide group in the molecule, that is, a polyfunctional tetracyclic ether compound, a compound having a plurality of thioether groups in the molecule, that is, a polyfunctional episulfide resin.

As the polyfunctional epoxy compound, there are epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; Varnish type epoxy resin; biphenol novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; Alicyclic epoxy resin; trihydroxytoluene type epoxy resin; alkylphenol type epoxy resin (for example, biguanide type epoxy resin); biphenol type epoxy resin; bisphenol S type epoxy resin; bisphenol A Novolak type epoxy resin; tetraphenyl Methane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl nonyl phenol resin; naphthyl group-containing epoxy resin; epoxy resin having dicyclopentadiene skeleton; Triphenylmethane type epoxy resin; epoxy resin having a sesquisesquioxane skeleton; glycidyl methacrylate copolymerized epoxy resin; copolymerization of cyclohexylmaleimide and glycidyl methacrylate Epoxy resin; epoxy-denatured polybutadiene rubber derivative; CTBN modified epoxy resin, etc., but is not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, especially triphenylmethane type epoxy resin, novolak type epoxy resin, bisphenol type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, biphenol novolac type ring An oxygen resin, a naphthalene type epoxy resin, or a mixture of these is preferred. By using (B) an epoxy resin having a sesquisesquioxane skeleton in combination with other epoxy resins, the glass transition temperature of the cured product can be increased.

In the curable resin composition of the present invention, the cured product has a maximum value of Tan δ of not more than 0.25 in a temperature range of 25 to 300 °C. As long as it is so physical, even if the temperature of the cured film is near Tg or above Tg, stable crack resistance can be obtained. Further, in the present specification, Tan δ is not particularly limited, that is, the resin layer after drying of the resin composition is irradiated with ultraviolet rays at about 500 mJ/cm ² , and further in a UV conveyor belt furnace equipped with a high-pressure mercury lamp at 1 J/ After the exposure amount of cm ² was irradiated, the physical properties of the cured product having a thickness of 40 μm obtained by completely curing the resin layer at 160 ° C for 60 minutes were obtained. Further, the ultraviolet ray is an electromagnetic wave having a wavelength of 10 to 400 nm. Tan δ is the value of the loss elastic modulus measured by the dynamic viscoelasticity measurement divided by the storage elastic modulus, that is, the loss tangent (= loss elastic modulus / storage elastic modulus). In the present specification, Tan δ is based on the frequency of 1 Hz, The obtained chart was measured from 25 ° C to 300 ° C under the conditions of a temperature increase rate of 5 ° C / min.

In order to obtain a cured product having a small Tan δ (= loss elastic modulus/storage elastic modulus), the loss elastic modulus (viscous component) may be lowered, or the storage elastic modulus (elastic component) may be increased, and two types may be obtained. In other words, in the hardened material, instead of adding a viscous component, it is better to increase the elastic component as much as possible. The means for setting the maximum value of Tan δ to less than 0.25 is not particularly limited.

The maximum value of Tan δ is less than 0.20, preferably 0.15 or less, and particularly preferably 0.13 or less, the crack resistance is further improved, which is preferable.

In addition, even when the compound having an ethylenically unsaturated group is blended by reducing the equivalent of the epoxy group of the thermosetting component of (B) epoxy resin or the like, even if the blending amount is made small, The Tan δ of the hardened material is reduced. (B) The epoxy group has an epoxy group equivalent of 400 g/eq.

When the maximum value of Tan δ of the hardened material is large, when the cured product is exposed to a high temperature, the viscous component in the hardened material is more likely to change and the physical properties are largely changed, but if the maximum value of Tan δ is less than 0.25, the cured product is even At a high temperature near the Tg of the cured product, the viscous component hardly changes, the physical property changes little, and the occurrence of cracks is more suppressed.

The curable resin composition of the present invention may be used by dry film formation or may be used as a liquid. When used as a liquid, it can also be 1 Liquid or two liquid or more.

Next, the dry film of the present invention has a resin layer obtained by coating and drying the curable resin composition of the present invention on a carrier film. When a dry film is formed, first, the curable resin composition of the present invention is diluted with the organic solvent and adjusted to an appropriate viscosity, and then a notch coater, a knife coater, a slit coater, a bar coater, An extrusion coater, a reverse coater, a transfer roller coater, a gravure coater, a spray coater, and the like are applied to a carrier film to have a uniform thickness. Thereafter, the coated composition is usually dried at a temperature of 40 to 130 ° C for 1 to 30 minutes, whereby a resin layer can be formed. The coating film thickness is not particularly limited, but the film thickness after drying is usually 3 to 150 μm, preferably within the range of 5 to 60 μm.

As the carrier film, a plastic film can be used, and a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, or a polystyrene can be used. Film and the like. The thickness of the carrier film is not particularly limited, and is generally appropriately selected within the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After the resin layer formed of the curable resin composition of the present invention is formed on the carrier film, it is preferable to prevent the dust from adhering to the surface of the resin layer, and further to cover the surface layer of the resin layer. As the cover film which can be peeled off, for example, a polyethylene film or a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As a cover film, when peeling off the cover film, as long as it is thinner than the resin layer and the load bearing The film's adhesion is small.

Further, in the present invention, the curable resin composition of the present invention may be applied onto the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface. In other words, in the case of producing a dry film in the present invention, any of a carrier film and a cover film may be used as the film for applying the curable resin composition of the present invention.

The printed wiring board of the present invention has a cured resin composition of the present invention or a cured product obtained from a resin layer of a dry film. In 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 the coating method by using the organic solvent, and is subjected to a liquid immersion coating method, a flow coating method, or a roll coating method. After the method such as a bar coating method, a screen printing method, or a curtain coating method is applied to a substrate, the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60 to 100 ° C. A non-stick resin layer. Also, when it is a dry film. After the resin layer is brought into contact with the substrate by a bonding machine or the like and bonded to the substrate, the carrier film is peeled off to form a resin layer on the substrate.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed of copper or the like in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/ Non-woven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin. Polyethylene. Polyphenylene oxide, polyoxybenzoic benzene. A material such as a copper-clad laminate for a high-frequency circuit such as a cyanate ester, and a copper-clad laminate of all grades (FR-4, etc.), and a metal substrate, a polyimide film, and a PET film. Polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, crystal Round plate, etc.

The volatilization drying after the application of the curable resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a heating plate, a convection oven, etc. (using a heat source having a steam-heated air method, the hot air in the dryer is used. This is done by a method of contacting the flow and a method of blowing the nozzle toward the support.

When the curable resin composition of the present invention is thermosetting, it can be thermally cured by, for example, heating to a temperature of 100 to 220 ° C, thereby forming heat resistance, chemical resistance, moisture absorption resistance, adhesion, electrical properties, and the like. A hardened film (hardened) with excellent properties.

When the curable resin composition of the present invention is photohardness, after forming a resin layer on a printed wiring board, the photomask formed with a specific pattern is selectively exposed by an active energy ray to dilute the unexposed portion. An aqueous solution (for example, 0.3 to 3% by mass of a carbonated soda aqueous solution) is developed to form a pattern of the cured product. Further, the cured product is irradiated with an active energy ray and then heat-hardened (for example, 100 to 220 ° C), or heated and cured, and then irradiated with an active energy ray, or only heat-hardened and hardened at the final stage (this hardening), thereby forming a dense A cured film excellent in properties such as properties and hardness. Further, when the curable resin composition of the present invention contains a photobase generating agent, it is preferably heated before development after exposure, and is heated as a heating condition before exposure after exposure, for example, at 60 to 150 ° C for 1 to 60 minutes. Preferably.

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

As the development method, a dip method, a shower method, a spray method, a brushing method, or the like can be used as the developing solution, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium citrate, or the like can be used. An aqueous solution of an alkali such as ammonia or an amine.

When the cured resin composition of the present invention is suitably used for forming a cured film on a printed wiring board, it is more suitably used for forming a permanent film, and is more preferably used for forming a solder resist, an interlayer insulating layer, or a cladding layer. In addition, since the cured resin composition of the present invention can obtain a cured product excellent in crack resistance and insulation reliability, it is suitable for forming a printed wiring board having a wiring pattern of a high-reliability fine pitch. Package substrate, especially permanent film for FC-BGA (especially solder resist).

Example

Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to the following examples. In addition, in the following, "parts" and "%" are all quality standards unless otherwise specified.

[Synthesis of carboxyl group-containing resin A-1]

Introduced 119.4 parts of novolac type cresol resin (Shownor CRG95 by Showa Polymer Co., Ltd., OH equivalent: 119.4) and 1.19 parts of potassium hydroxide in an autoclave equipped with a thermometer, a nitrogen gas introduction device, an alkylene oxide introduction device, and a stirring device. Further, 119.4 parts of toluene was replaced with nitrogen in the system while stirring, and the temperature was raised by heating. Subsequently, 63.8 parts of propylene oxide was slowly dropped, and the mixture was reacted at 0 to 4.8 kg/cm ² at 125 to 132 ° C for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to the reaction solution and mixed, and potassium hydroxide was neutralized to obtain a nonvolatile matter of 62.1%, and a hydroxyl group value of 182.2 mgKOH/g (307.9 g/eq.). A propylene oxide reaction solution of a novolac type cresol resin. This is an average of 1.08 moles of propylene oxide per equivalent of 1 phenolic hydroxyl group.

293.0 parts of a propylene oxide reaction solution of the obtained novolac 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 blowing tube. In the middle, air was blown at a rate of 10 ml/min, and the mixture was reacted at 110 ° C for 12 hours while stirring. The water formed by the reaction, as an azeotropic mixture with toluene, distilled off 12.6 parts of water.

Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, followed by washing with water. Thereafter, 118.1 parts of toluene ethylene glycol monoethyl ether acetate was replaced with toluene in an evaporator, and the mixture was distilled off to obtain a novolac type acrylate resin solution. Next, will 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 blowing tube, and air was blown at a rate of 10 ml/min, and while stirring, slowly 60.8 parts of tetrahydrophthalic anhydride was added thereto, and the mixture was reacted at 95 to 101 ° C for 6 hours, and then taken out after cooling. Thus, a solution of a photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and an acid value of a solid component of 87.7 mgKOH/g was obtained. Hereinafter, the solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-1.

[Synthesis of carboxyl group-containing resin A-2]

456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formaldehyde solution were placed in a flask equipped with a cooling tube and a stirrer, and the temperature was maintained at 40 ° C or lower, and 228 parts of a 25% sodium hydroxide solution was added. The reaction was carried out at ° C for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C, and while maintaining at 40 ° C or lower, it was neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution. The separated aqueous layer is then separated. After the separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, and then washed three times with 500 parts of distilled water, and water, a solvent, and the like were removed under reduced pressure at a temperature of 50 ° C or lower. The obtained methylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of a methylol compound.

After a part of the obtained methanol solution of the methylol compound was dried in a vacuum dryer at room temperature, the solid content was 55.2%. Into a flask equipped with a cooling tube and a stirrer, 500 parts of a methanol solution of the obtained methylol compound and 440 parts of 2,6-xylenol were placed, and the mixture was uniformly dissolved at 50 °C. After uniformly dissolving, methanol was removed under reduced pressure at a temperature below 50 °C. Add grass after 8 parts of acid was reacted at 100 ° C for 10 hours. After completion of the reaction, the distilled portion was removed under reduced pressure of 180 ° C and 50 mmHg to obtain 550 parts of novolak resin A.

130 parts of novolak resin A, 2.6 parts of 50% sodium hydroxide solution, toluene/methyl isobutyl ketone (mass ratio = 2) were placed in an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device. /1) 100 parts, the system was replaced with nitrogen while stirring, and then the temperature was raised by heating, and 60 parts of propylene oxide was gradually introduced at 150 ° C and 8 kg / cm ² to cause a reaction. The reaction was continued for about 4 hours until the gauge pressure became 0.0 kg/cm ^{2 and} then cooled to room temperature. To the reaction solution, 3.3 parts of a 36% aqueous hydrochloric acid solution was added and mixed, and sodium hydroxide was neutralized. The neutralization reaction product was diluted with toluene, washed with water three times, and desolventized with an evaporator to obtain a propylene oxide adduct of a novolac resin A having a hydroxyl group of 189 g/eq. This is one equivalent per phenolic hydroxyl group and has an average addition of 1 mole of propylene oxide.

189 parts of the propylene oxide adduct of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 140 parts of toluene were placed in a mixer, a thermometer, and an air blowing tube. In the reactor, the mixture was stirred while being blown with air, and the temperature was raised to 115 ° C. The water formed by the reaction and the toluene were used as an azeotropic mixture, and the mixture was further distilled for 4 hours, and then cooled to room temperature. The obtained reaction solution was washed with water using a 5% NaCl aqueous solution, and the toluene was removed by distillation under reduced pressure, and then diethylene glycol monoethyl ether acetate was added to obtain a 67% solid acrylate resin solution.

Next, placed in a 4-neck flask with a stirrer and a reflow cooler 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine, the mixture was heated to 110 ° C, 60 parts of tetrahydrophthalic anhydride was added, and the reaction was allowed to proceed for 4 hours, and cooled. Remove afterwards. The photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and a solid content of 81 mgKOH/g. Hereinafter, the solution of the photosensitive resin containing a carboxyl group is referred to as a resin solution A-2.

[Synthesis of carboxyl group-containing resin A-3]

Into 600 g of diethylene glycol monoethyl ether acetate, n-cresol novolac type epoxy resin (EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average functional group number 7.6) 1070 g (made by DIC Corporation) was placed ( The glycidyl group (total number of aromatic rings): 5.0 moles, 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were heated to 100 ° C and stirred to dissolve uniformly. Next, 4.3 g of triphenylphosphine was placed, and after heating to 110 ° C and reacting for 2 hours, the temperature was raised to 120 ° C and the reaction was further carried out for 12 hours. Into the obtained reaction liquid, 415 g of an aromatic hydrocarbon (Solvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were placed, and the reaction was carried out at 110 ° C for 4 hours, and after cooling, a photosensitive carboxyl group was obtained. Resin solution. The resin solution thus obtained had a solid content of 65% and an acid value of a solid component of 89 mgKOH/g. Hereinafter, the solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-3.

[Synthesis of carboxyl group-containing resin A-4]

With thermometer, mixer, drip funnel, and reflow cooler In the flask, dipropylene glycol monomethyl ether 325.0 as a solvent was heated to 110 ° C, 174.0 parts of methacrylic acid, ε-caprolactone modified methacrylic acid (average molecular weight 314) 174.0 parts, and methyl methacrylate 77.0 parts. 222.0 parts of dipropylene glycol monomethyl ether and 12.0 parts of t-butyl peroxy 2-ethyl hexanoate (Perbutyl O, manufactured by Nippon Oil Co., Ltd.) as a polymerization catalyst were dropped over 3 hours, and further After stirring at 110 ° C for 3 hours, the polymerization catalyst was deactivated to obtain a resin solution.

After cooling the resin solution, 289.0 parts of Cyclomer A200 manufactured by Daicel Chemical Industry Co., Ltd., 3.0 parts of triphenylphosphine, and 1.3 parts of hydroquinone monomethyl ether were added, and the temperature was raised to 100 ° C, and ring-opening addition of an epoxy group was carried out by stirring. The reaction was carried out to obtain a photosensitive carboxyl group-containing resin solution. The weight average molecular weight (Mw) of the resin solution thus obtained was 15,000, and the solid content was 57%, and the acid value of the solid matter was 79.8 mgKOH/g. Hereinafter, the solution of the carboxyl group-containing photosensitive resin is referred to as a resin solution A-4.

[Synthesis of epoxy resin B-1 having a sesquioxane skeleton]

90.0 parts of γ-glycidoxypropyltrimethoxydecane and 93 parts of methyl isobutyl ketone were placed in a reaction vessel, and the temperature was raised to 80 °C. After the temperature was raised, 21.6 parts of a 0.1% by weight potassium hydroxide aqueous solution was continuously dropped over a period of 30 minutes. After the completion of the dropwise addition, the produced methanol was reacted at 80 ° C for 5 hours while removing. After the completion of the reaction, the washing was repeated until the washing liquid became neutral. Next, by removing the solvent under reduced pressure, 69 parts of an epoxy resin having a sesquiterpene skeleton was obtained. The epoxy resin obtained had an epoxy equivalent of 165 g/eq. and a weight average molecular weight of 2,000.

[Synthesis of epoxy resin B-2 having a sesquioxane skeleton]

90.0 parts of γ-glycidoxypropyltrimethoxydecane, 3.0 parts of phenyltrimethoxydecane, 2.0 parts of methyltrimethoxydecane, and 93 parts of methyl isobutyl ketone were placed in a reaction vessel, and the temperature was raised to 80 ° C. . After the temperature was raised, 21.6 parts of a 0.1% by weight potassium hydroxide aqueous solution was continuously dropped over a period of 30 minutes. After the completion of the dropwise addition, the produced methanol was reacted at 80 ° C for 5 hours while removing. After the completion of the reaction, the washing was repeated until the washing liquid became neutral. Next, by removing the solvent under reduced pressure, 69 parts of an epoxy resin having a sesquiterpene skeleton was obtained. The epoxy resin obtained had an epoxy equivalent of 176 g/eq. and a weight average molecular weight of 2,200.

[Synthesis of epoxy resin B-3 having a sesquioxane skeleton]

65.0 parts of γ-glycidoxypropyltrimethoxydecane, 12.0 parts of phenyltrimethoxydecane, 8.0 parts of methyltrimethoxydecane, and 93 parts of methyl isobutyl ketone were placed in a reaction vessel, and the temperature was raised to 80 ° C. . After the temperature was raised, 21.6 parts of a 0.1% by weight potassium hydroxide aqueous solution was continuously dropped over a period of 30 minutes. After the completion of the dropwise addition, the produced methanol was reacted at 80 ° C for 5 hours while removing. After the completion of the reaction, the washing was repeated until the washing liquid became neutral. Next, by removing the solvent under reduced pressure, 69 parts of an epoxy resin having a sesquiterpene skeleton was obtained. The epoxy resin obtained had an epoxy equivalent of 236 g/eq. and a weight average molecular weight of 2,200.

[Synthesis of epoxy resin B-4 having a sesquioxane skeleton]

40.0 parts of γ-glycidoxypropyltrimethoxydecane, 25.0 parts of phenyltrimethoxydecane, 15.0 parts of methyltrimethoxydecane, and 93 parts of methyl isobutyl ketone were placed in a reaction vessel, and the temperature was raised to 80 ° C. . After the temperature was raised, 21.6 parts of a 0.1% by weight potassium hydroxide aqueous solution was continuously dropped over a period of 30 minutes. After the completion of the dropwise addition, the produced methanol was reacted at 80 ° C for 5 hours while removing. After the completion of the reaction, the washing was repeated until the washing liquid became neutral. Next, by removing the solvent under reduced pressure, 69 parts of an epoxy resin having a sesquiterpene skeleton was obtained. The epoxy resin obtained had an epoxy equivalent of 400 g/eq. and a weight average molecular weight of 2,200.

[Adjustment of surface treated inorganic filler (cerium oxide) C-1]

70 g of spherical cerium oxide (SFP-20M manufactured by Denka Co., Ltd.), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of a decane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed. The cerium oxide solvent dispersion D-1 was obtained.

[Adjustment of surface treated inorganic filler (barium sulfate) C-2]

Barium sulfate (B-30 (aluminum oxide surface treated barium sulfate) manufactured by Seiko Chemical Industry Co., Ltd.) was uniformly dispersed in 70 g, and PMA (propylene glycol monomethyl ether acetate) as a solvent (28 g) and a dispersing agent (manufactured by BYK Corporation) BYK-111) 2g, a barium sulfate solvent dispersion D-2 was obtained.

[Adjustment of surface treated cerium oxide]

Uniform dispersion of spherical cerium oxide (SFP-made by Denka) 20 M) 70 g, 2 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 2 g of a dispersing agent (BYK-111 manufactured by BYK Co., Ltd.) to obtain a cerium oxide solvent dispersion.

[Examples 1 to 16 and Comparative Examples 1 to 5]

The resin solution (varnish) described above was blended with the various components shown in Table 1 in the ratio (parts by mass) shown in Table 1, and prepared by mixing with a stirrer, followed by kneading in three rolls to prepare a curable resin. Composition.

<glass transition temperature Tg and thermal expansion coefficient CTE> (Examples 1 to 15, Comparative Examples 1 to 5)

The curable resin composition was entirely applied by screen printing on a copper foil substrate to have a dry film thickness of about 40 μm. This was dried at 80 ° C, and cooled to room temperature to form a resin layer of a curable resin composition, and an evaluation substrate having an uncured sample of each of Examples and Comparative Examples was obtained. This was exposed by HMW 680 GW (metal halide bulb, scattered light) manufactured by ORC Co., Ltd. and with an optimum exposure amount: 800 Mj by a negative image of 50 mm × 3 mm strip. Thereafter, development was carried out with a 1 wt.% sodium carbonate aqueous solution at 30 ° C to obtain a pattern of the cured film. Further, after the integrated exposure amount was set to 1000 mJ and ultraviolet rays were irradiated, the film was heated at 160 ° C for 1 hour and hardened.

The cured film of the evaluation substrate obtained above was peeled off from the copper foil, and evaluation was performed. The measurement was performed using a TMA measuring apparatus (manufactured by Shimadzu Corporation, model name: TMA6000), and evaluated for Tg and CTEα1 (0° C. to 50° C.) and CTE α 2 (200° C. to 250° C.). Evaluation criteria are as follows Said.

(Embodiment 16)

The curable resin composition was completely applied by screen printing on a copper foil substrate to a dry film thickness of about 40 μm. This was dried at 80 ° C, and allowed to cool to room temperature to form a resin layer of a curable resin composition. This was heated at 160 ° C for 1 hour to be hardened to obtain an evaluation substrate having a cured film. The cured film of the evaluation substrate obtained above was peeled off from the copper foil, and a strip of 50 mm × 3 mm was cut out to carry out evaluation. The measurement was performed using a TMA measuring apparatus (manufactured by Shimadzu Corporation, model name: TMA6000), and evaluated for Tg and CTEα1 (0° C. to 50° C.) and CTE α 2 (200° C. to 250° C.). The evaluation criteria are as follows.

(Tg)

◎...150°C or more

○...145°C or more and less than 150°C

△...140°C or more and less than 145°C

×... less than 140 ° C

(CTEα1)

◎... less than 40ppm

○...40ppm or more and less than 50ppm

△...50ppm or more and less than 60ppm

×...60ppm or more

(CTEα2)

◎... less than 110ppm

○...110ppm or more and less than 120ppm

△...120ppm or more and less than 130ppm

×...130ppm or more

<elasticity E and Tan δ> (Examples 1 to 15 and Comparative Examples 1 to 5)

The curable resin composition was entirely coated on the copper foil substrate by screen printing to have a dried film thickness of about 40 μm. This was dried at 80 ° C, and cooled to room temperature to form a resin layer of a curable resin composition, and an evaluation substrate having an uncured sample of each of Examples and Comparative Examples was obtained. This was exposed by HMW 680 GW (metal halide bulb, scattered light) manufactured by ORC Corporation and passed through a strip of negative light of 50 mm × 5 mm at 800 mJ. Thereafter, development was carried out with a 1 wt.% sodium carbonate aqueous solution at 30 ° C to obtain a pattern of the cured film. Further, the integrated exposure amount was irradiated with ultraviolet rays at 1000 mJ, and then heat-hardened at 160 ° C for 1 hour to obtain an evaluation substrate having a cured film.

The hardened film of the evaluation substrate obtained above was peeled off from the copper foil, and evaluation was performed. The measurement was performed using a DMA measuring apparatus (model name: DMS6100 manufactured by Shimadzu Corporation), and evaluated for E at 260 °C. For Tan δ, the temperature was raised from 25 ° C to 300 ° C in DMS6100 manufactured by Hitachi Hightech Co., Ltd., and the sine wave mode was extended at 5 ° C / min, frequency 1 Hz. Determine by the formula to obtain the maximum value in the field of temperature measurement.

(Embodiment 16)

The curable resin composition was entirely coated on the copper foil substrate by screen printing to have a dried film thickness of about 40 μm. This was heat-hardened at 160 ° C for 1 hour to obtain an evaluation substrate having a cured film. The hardened film of the evaluation substrate obtained above was peeled off from the copper foil, and evaluation was performed. The measurement was performed using a DMA measuring apparatus (model name: DMS6100 manufactured by Shimadzu Corporation), and evaluated for E at 260 °C. The Tan δ was heated from 25 ° C to 300 ° C in a DMS 6100 manufactured by Hitachi Hightech Co., Ltd., and measured at a 5 ° C/min, frequency 1 Hz, and extended sine wave mode to obtain the maximum value in the field of temperature measurement.

The evaluation criteria are as follows.

(elasticity E)

◎...1×10 ⁹ Pa or more

○...5×10 ⁸ Pa or more and less than 1×10 ⁹ Pa

△...1×10 ⁸ Pa or more and less than 5×10 ⁸ Pa

×... less than 1 × 10 ⁸ Pa

(Tanδ)

◎... less than 0.20

○...0.20 or more and less than 0.25

△...0.25 or more and less than 0.30

×...0.30 or more

<warp> (Examples 1 to 15 and Comparative Examples 1 to 5)

The curable resin composition was completely applied by screen printing on a CZ-treated 35 μm copper foil substrate to have a dried film thickness of 20 μm. This was dried at 80 ° C, and cooled to room temperature to form a resin layer of a curable resin composition, and an evaluation substrate having an uncured sample of each of Examples and Comparative Examples was obtained. In this case, HMW 680GW (metal halide bulb, scattered light) manufactured by ORC Corporation was used and the overall exposure was performed at an optimum exposure amount: 800 mJ. Thereafter, development treatment was carried out with a 1 wt.% sodium carbonate aqueous solution at 30 ° C to obtain a pattern of the cured film. Further, the integrated exposure amount was irradiated with ultraviolet rays at 1000 mJ, and then heated at 160 ° C for 1 hour to be cured.

The cured film of the evaluation substrate obtained above was cut out to 50 mm × 50 mm, and the cured film was faced downward, and was placed on a horizontal countertop. After standing, the distance from the water platform surface to the Cu foil was measured for each of the four corners of the cut cured film, and the average value was determined and evaluated as described below.

(Embodiment 16)

The curable resin composition was completely applied by screen printing on a CZ-treated 35 μm copper foil substrate to have a dried film thickness of 20 μm. This was dried at 80 ° C and cooled to room temperature to form a resin layer of a curable resin composition. This was heated at 160 ° C for 1 hour and hardened to obtain an evaluation substrate having a cured film.

The cured film of the evaluation substrate obtained above was cut out to 50 mm × 50 mm, and the cured film was faced downward, and was placed on a horizontal countertop. After standing, the distance from the water platform surface to the Cu foil was measured for each of the four corners of the cut cured film, and the average value was determined and evaluated as described below.

◎... less than 10mm

○...10mm or more and less than 15mm

△...15mm or more and less than 20mm

×...20mm or more

<reaction rate> (Examples 1 to 15 and Comparative Examples 1 to 5)

The electroplated copper substrate was treated with CZ8101 at an etching rate of 1 μm/m ² , and the curable resin composition was entirely coated on the surface by screen printing to have a dried film thickness of about 20 μm. This was dried at 80 ° C, and cooled to room temperature to form a resin layer of a curable resin composition, thereby obtaining an evaluation substrate α. In this case, HMW 680GW (metal halide bulb, scattered light) manufactured by ORC Corporation was used and the overall exposure was performed at an optimum exposure amount: 800 mJ. Thereafter, it was treated with a 1 wt.% aqueous sodium carbonate solution at 30 ° C to obtain a cured film. Further, after the integrated exposure amount was irradiated with ultraviolet rays at 1000 mJ, the film was heated and hardened under the following conditions to obtain an evaluation substrate β. The FT-IR measurement of the substrates α and β obtained as described above was carried out, and the reaction rate of the epoxy group was measured. The reaction rate of the epoxy group was calculated using a Microscope spotlight 200 as a measuring device, and the peak height in the vicinity of 913 cm ^-1 from the vibration of the epoxy group was calculated.

(Embodiment 16)

The electroplated copper substrate was treated with CZ8101 at an etching rate of 1 μm/m ² , and the curable resin composition was entirely coated on the surface by screen printing to have a dried film thickness of about 20 μm. This was dried at 80 ° C, and cooled to room temperature to form a resin layer of a curable resin composition, thereby obtaining an evaluation substrate α. This was heated and hardened under the following conditions to obtain an evaluation substrate β. The FT-IR measurement of the substrates α and β obtained as described above was carried out, and the reaction rate of the epoxy group was measured. The reaction rate of the epoxy group was calculated using a Microscope spot light 200 as a measuring device, and the peak height in the vicinity of 913 cm ^-1 from the vibration of the epoxy group was calculated.

◎...150 ° C 60min hardening reaction rate of 98% or more

○...160°C 60min hardening reaction rate of 98% or more

△...170 ° C 60min hardening reaction rate of 98% or more

×...170°C The reaction rate of epoxy under 60min hardening is less than 98%

<Resolution Evaluation> (Examples 1 to 15 and Comparative Examples 1 to 5)

The electroplated copper substrate was treated with CZ8101 at an etching rate of 1 μm/m ² , and the curable resin composition was entirely coated on the surface by screen printing to have a dried film thickness of about 20 μm. This was dried at 80 ° C and cooled to room temperature to form a resin layer of a curable resin composition. In this regard, HMW 680GW (metal halide bulb, scattered light) manufactured by ORC Corporation was used and pattern exposure was performed at an optimum amount of violence: 800 mJ. Thereafter, development was carried out with a 1 wt.% sodium carbonate aqueous solution at 30 ° C to obtain a pattern of the cured film. Further, the integrated exposure amount was irradiated with ultraviolet rays at 1000 mJ, and then heated at 160 ° C for 1 hour to be cured.

The opening diameter of the evaluation substrate obtained above was observed to confirm whether or not a halo, a cavity was generated and evaluated.

◎...with a good opening diameter at 50μm

○...with a good opening diameter at 70μm

△...with a good opening diameter at 100μm

×...100μm could not get a good opening diameter or could not be imaged

<Insulation reliability (HAST tolerance)> (Examples 1 to 15 and Comparative Examples 1 to 5)

Using a substrate having a comb pattern of L/S = 20/20, the curable resin composition was completely coated by screen printing to have a dried film thickness of about 20 μm. This was dried at 80 ° C, and cooled to room temperature to form a resin layer of a curable resin composition, and an evaluation substrate having an uncured sample of each of Examples and Comparative Examples was obtained. In this case, HMW 680GW (metal halide bulb, scattered light) manufactured by ORC Corporation was used and the overall exposure was performed at an optimum exposure amount: 800 mJ. Thereafter, development was carried out with a 1 wt.% sodium carbonate aqueous solution at 30 ° C to obtain a pattern of the cured film. Further, the integrated exposure amount was irradiated with ultraviolet rays at 1000 mJ, and then heated at 160 ° C for 1 hour to be cured. Then, the obtained evaluation substrate was connected to an electrode, and placed in a high-temperature and high-humidity bath at an environment of 130 ° C and a humidity of 85%, and subjected to a HAST test at a voltage of 5 V, and the time when the electrical insulating property was 1 × 10 ⁶ Ω or less was measured. .

(Embodiment 16)

Using a substrate having a comb pattern of L/S = 20/20, the curable resin composition was completely coated by screen printing to have a dried film thickness of about 20 μm. This was dried at 80 ° C and cooled to room temperature to form a resin layer of a curable resin composition. This was heated at 160 ° C for 1 hour and hardened to obtain an evaluation substrate having a cured film. Then, the obtained evaluation substrate was connected to an electrode, and placed in a high-temperature and high-humidity bath at an environment of 130 ° C and a humidity of 85%, and subjected to a HAST test at a voltage of 5 V, and the time when the electrical insulating property was 1 × 10 ⁶ Ω or less was measured. .

◎...300h pass

○...200h pass

△...150h pass

×...150h or less for NG

<Crack tolerance (TCT tolerance)> (Examples 1 to 15 and Comparative Examples 1 to 5)

The curable resin composition was completely coated on the evaluation substrate for FC-BGA formed at a pitch of 250 μm. This was dried and cooled to room temperature to form a resin layer of a curable resin composition. For this purpose, direct imaging exposure was performed with an optimum exposure: 800 mJ and an opening size of SRO (Solder Resist Opening) 80 μm on a copper pad. Thereafter, a 1 wt% sodium carbonate aqueous solution at 30 ° C was developed by spraying to obtain a pattern of the cured film. Further, the integrated exposure amount was irradiated with ultraviolet rays at 1000 mJ, and then heated at 160 ° C for 1 hour to be cured. After that, Au plating Processing, solder bump formation, mounting of Si wafers, and evaluation of substrates.

The evaluation substrate obtained above was placed in a thermal cycler which was subjected to temperature cycling between -65 ° C and 150 ° C to carry out a TCT (Thermal Cycle Test). Further, the surfaces of the cured film at 600 cycles, 800 cycles, and 1000 cycles were observed. The criterion is as follows.

(Embodiment 16)

The curable resin composition was completely coated on the evaluation substrate for FC-BGA formed at a pitch of 250 μm. This was dried and cooled to room temperature to form a resin layer of a curable resin composition. This was heated at 160 ° C for 1 hour and hardened to obtain a substrate having a cured film. On the other hand, a CO ₂ laser processing machine (manufactured by Hitachi Biomechanics Co., Ltd.) was used to form a passage on the cured film to have a tip diameter of 80 μm. Thereafter, Au plating treatment, solder bump formation, and Si wafer mounting were carried out to obtain an evaluation substrate.

The evaluation substrate obtained above was placed in a thermal cycler which was subjected to temperature cycling between -65 ° C and 150 ° C to carry out a TCT (Thermal Cycle Test). Further, the surfaces of the cured film at 600 cycles, 800 cycles, and 1000 cycles were observed. The criterion is as follows.

◎...1000 cycles without abnormalities

○...800 cycles without abnormality, 1000 cycles and cracking

△...600 cycles without abnormality, 800 cycles and cracking

×...600 cycles and cracking

*1: The carboxyl group-containing resin solution A-1 synthesized above

*2: The carboxyl group-containing resin solution A-2 synthesized above

*3: The carboxyl group-containing resin solution A-3 synthesized above

*4: The above-mentioned carboxyl group-containing resin solution A-4

*5: Irgacure TPO (2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide) manufactured by BASF JAPAN

*6: Irgacure 907 (2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one) manufactured by BASF JAPAN

*7: Irgacure OXE02 (ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl)-9H-carbazolyl-3-yl]-1-(o-acetamidine) manufactured by BASF JAPAN肟)

*8: The epoxy resin B-1 having the sesquisesquioxane skeleton synthesized as described above

*9: The epoxy resin B-2 having the sesquisesquioxane skeleton synthesized above

*10: The epoxy resin B-3 having the sesquisesquioxane skeleton synthesized above

*11: The epoxy resin B-4 having the sesquisesquioxane skeleton synthesized above

*12: jER828 (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation

*13: DEN431 (phenol novolac epoxy resin) manufactured by Dow Chemical Co., Ltd.

*14: N-870 75EA (bisphenol A novolac type epoxy resin) manufactured by DIC Corporation

*15: EXA-724 (triphenylmethane type epoxy resin) manufactured by DIC Corporation)

*16: The surface treated cerium oxide solvent dispersion C-1 (the spherical cerium oxide was uniformly dispersed to PMA. The surface treatment of propylene oxide. The content of cerium oxide was 70% by weight (solid content).矽 average particle size 0.8μm)

*17: The surface treated barium sulfate solvent dispersion C-2 (the barium sulfate was uniformly dispersed to PMA. The surface treatment of alumina. The content of barium sulfate was 70% by weight (solid content). The average particle size of barium sulfate (0.5) Mm))

*18: The above-mentioned adjusted cerium oxide solvent dispersion without surface treatment (spherical cerium oxide is uniformly dispersed to PMA. No surface treatment. The content of cerium oxide is 70% by weight (solid content). Trail 0.8μm)

*19: Disperse the settled barium sulfate uniformly to the PMA. The barium sulfate content is 70% by weight (solid content). No surface treatment.

*20: DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd.

*21: Blue colorant, colorant content 12% by mass

*22: yellow colorant, colorant content 10% by mass

*23: DICY (dicyandiamine)

*24: Not evaluated

From the results shown in the above table, it is understood that the cured product of the curable resin composition of Examples 1 to 16 of the present invention is excellent in crack resistance and insulation reliability. On the other hand, when the curable resin composition of Comparative Examples 1 to 5 is used, the elastic modulus (E) at a high temperature is particularly low, and it is difficult to obtain high crack resistance and insulation reliability.

Claims (8)

A curable resin composition comprising (A) a carboxyl group-containing resin and (B) an epoxy resin having a sesquisesquioxane skeleton. The curable resin composition of claim 1, further comprising (C) a surface-treated inorganic filler. The curable resin composition of claim 1, wherein the (A) carboxyl group-containing resin has a structure represented by the following general formula (1). (wherein R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group, and k represents a value of any of 0.3 to 10). The curable resin composition of claim 1, wherein the (A) carboxyl group-containing resin has a structure represented by the following general formula (2), (wherein R ⁵ to R ⁷ each independently represent a hydrogen atom or an alkyl group, Z represents an acid anhydride residue, and m represents a value of any of 0.3 to 10). The curable resin composition of claim 1, wherein the epoxy resin having the sesquisesquioxane skeleton (B) has a structure represented by the following general formula (3), (wherein R ⁸ to R ¹¹ are each independently a group having an SiO bond or an organic group, and at least one of R ⁸ to R ¹¹ is a group having an epoxy group). A dry film comprising a resin layer obtained by applying a curable resin composition according to claim 1 to a film and drying the film. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 5 or the resin layer of the dry film of claim 6. A printed wiring board characterized by having a cured product as claimed in claim 7.