KR102369508B1 - Curable resin composition, dry film, cured product and printed wiring board - Google Patents

Abstract

A curable resin composition and the like capable of obtaining a cured product having excellent crack resistance when subjected to a high-temperature load are provided. A resin composition comprising (A) an alkali-soluble resin, (B) a thermosetting component, (C) a compound having an ethylenically unsaturated group, (D) a photoinitiator, and (E) a surface-treated inorganic filler, wherein (E) The inorganic filler has an average particle diameter of 100 nm to 1 µm, and has a reactive group capable of reacting with at least any one of the (A) alkali-soluble resin, the (B) thermosetting component, and the (C) compound having an ethylenically unsaturated group , As the (B) thermosetting component, an epoxy equivalent of 300 g/eq. Tanδ in the case of dynamic viscoelasticity measurement from 25°C to 300°C under the conditions of a frequency of 1Hz and a temperature increase rate of 5°C/min in a cured product having a thickness of 40 μm obtained from the resin composition containing the following epoxy resins The maximum value is 0.15 or less, The curable resin composition etc. characterized by the above-mentioned.

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.

In recent years, with the rapid progress of semiconductor components, electronic devices tend to be lightweight, thin, compact, high-performance, and multifunctional. In keeping with this trend, miniaturization and multi-pinning of semiconductor packages are being put to practical use.

Specifically, instead of IC packages called QFP (quad flat pack package) and SOP (small outline package), BGA (ball grid array), CSP (chip scale package), etc. A so-called IC package is being used. In recent years, FC-BGA (flip chip ball grid array) has also been put to practical use as an IC package with higher density. In printed wiring boards (also referred to as package boards) used in such IC packages, the pitch of Solder Resist Opening (SRO) is narrow and they are formed close to each other, so the solder resist formed between the SROs becomes fine and thin and cracks occur. it's getting easier

In the future, while thinning of the solder resist proceeds, heat generation of mounted components tends to increase, so crack resistance at a higher temperature is required. In particular, in-vehicle components have a high current density and are prone to high temperatures, so their use in an environment prone to cracking is a prerequisite.

Conventionally, as a method of improving crack resistance, the photocurable resin composition containing, for example, an acid-modified vinyl group containing epoxy resin, an elastomer, a photoinitiator, a diluent, and a hardening|curing agent is disclosed (for example, patent document 1). It is disclosed by this patent document 1 that crack resistance improves by an elastomer.

However, only with the above means, satisfactory results could not be obtained when crack resistance in a higher temperature state is required in the future.

Japanese Patent Laid-Open No. 11-240930

Therefore, an object of the present invention is a curable resin composition capable of obtaining a cured product having excellent crack resistance when subjected to a high temperature load, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film , and to provide a printed wiring board having the cured product.

Various stresses are applied to the solder resist used in the IC package, and the stress that has become unbearable due to the accumulation of these stresses is released as cracks.

The stress is mainly: (1) the stress generated by the difference in thermal linear expansion (CTE) between the solder resist and peripheral members (copper, substrate, etc.), and (2) the gas generated by the thermal history during packaging (solder resist and substrate). There are stress (distortion) caused by a crosslinking reaction in the solder resist due to a heat history after mounting and (3) stress caused by gas and moisture). Conventionally, in order to suppress cracks, the method of mixing|blending an elastomer etc. with a soldering resist to relieve stress, and the method of reducing the high dielectric transition temperature (Tg) and CTE of a soldering resist with respect to the stress generated in said (1). It worked.

However, in recent years, since IC packages for in-vehicle applications are exposed to high-temperature environments, the stress caused by (2) and (3) is increased by the influence of the temperature environment, thermal history, and members used. Since it is infinite, simple stress relaxation and high Tg and low CTE may not be able to prevent the occurrence of stress.

So, in the first place, the inventors have, in addition to means for lowering the coefficient of thermal expansion after curing with respect to the solder resist in which the coefficient of thermal expansion and the modulus of elasticity are changed due to heat, after curing, the elastic modulus is lowered at Tg or more. A force proportional to the displacement rate It was found that evaluation of the viscoelasticity of DMA taking into account (viscosity) is necessary. The behavior of the viscous component by this DMA becomes a very important physical property in order to predict the characteristic of a soldering resist whose Tg is lower than the melting temperature of solder.

In particular, the change behavior of Tanδ obtained by DMA has important meaning, and a material with a large maximum value of the peak of Tanδ (for example, a material having physical properties as shown in FIG. 1) is mechanically For the purpose of relieving stress, it is considered suitable for members requiring softness and flexibility. On the other hand, a material with a small maximum value of the Tanδ peak (for example, a material having physical properties as shown in FIG. 2) is not weakened by stress. It was found to be rigid and to have little temperature dependence.

In addition, the latter method needs to be considered for future IC packages, that is, if the value of Tanδ of DMA is 0.15 or less, the viscous component in the cured product is small. It is possible to suppress the occurrence of changes in physical properties due to sparse cross-linked structures due to molecular motion in the vicinity. That is, since the temperature dependence is small and the change in physical properties before and after Tg is small, the stress generated due to the change in the physical properties due to the high temperature heat history can be reduced. Therefore, when the value of Tanδ of DMA is 0.15 or less, it is effective not only for the stress in (1) above, but also in suppressing the stress in (3).

In addition, in order to reduce Tanδ of the cured product, the average particle diameter of the inorganic filler is set within a specific range, and a specific reactive group is introduced into the inorganic filler, and the epoxy equivalent of the epoxy resin is within a range of a specific value or less, thereby making crosslinking dense. was found to be effective for the stress in (2).

That is, the curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a thermosetting component, (C) a compound having an ethylenically unsaturated group, (D) a photoinitiator, and (E) a surface-treated inorganic filler. As a resin composition containing, said (E) surface-treated inorganic filler has an average particle diameter of 100 nm - 1 micrometer, and said (A) alkali-soluble resin, said (B) thermosetting component, and said (C) ethylenically unsaturated group It has a reactive group which can react with at least any 1 sort(s) of the compound which has, and as said (B) thermosetting component, epoxy equivalent 300g/eq. Tanδ in the case of dynamic viscoelasticity measurement from 25°C to 300°C under the conditions of a frequency of 1Hz and a temperature increase rate of 5°C/min in a cured product having a thickness of 40 μm obtained from the resin composition containing the following epoxy resins It is characterized in that the maximum value is 0.15 or less.

The curable resin composition of the present invention has an epoxy equivalent of 300 g/eq. As the following epoxy resins, it is preferable to include (B-1) a bifunctional or more functional epoxy resin having a softening point of 40°C or less, and (B-2) a bifunctional or more functional epoxy resin having a softening point of 40°C or less.

As for the curable resin composition of this invention, it is preferable that the compounding quantity of the compound which has the said (C) ethylenically unsaturated group is less than 20 mass parts with respect to 100 mass parts of said (A) alkali-soluble resins.

As for the curable resin composition of this invention, it is preferable that the compounding quantity of the said (E) surface-treated inorganic filler is 35 mass % or more in solid content of curable resin composition.

The curable resin composition of the present invention has a storage elastic modulus of 1 GPa or more at 150° C. when dynamic viscoelasticity is measured from 25° C. to 300° C. under conditions of a frequency of 1 Hz and a temperature increase rate of 5° C./min of the cured product. It is preferable that the rate of change of the storage elastic modulus from °C to 150 °C is within 70%.

As for the curable resin composition of this invention, it is preferable that CTE?2 of the said hardened|cured material is 110 ppm or less.

As for the curable resin composition of this invention, it is preferable that Tg of the said hardened|cured material is 160 degreeC or more.

It is preferable that curable resin composition of this invention is for soldering resist formation.

The dry film of this invention has a resin layer obtained by apply|coating and drying the said curable resin composition to a film, It is characterized by the above-mentioned.

The hardened|cured material of this invention is obtained by hardening|curing the resin layer of the said curable resin composition or the said dry film, It is characterized by the above-mentioned.

The printed wiring board of this invention has the said hardened|cured material, It is characterized by the above-mentioned.

According to the present invention, a curable resin composition capable of obtaining a cured product having excellent crack resistance when subjected to a high-temperature load, a dry film having a resin layer obtained from the composition, a cured product of the resin layer of the composition or the dry film, and The printed wiring board which has this hardened|cured material can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is an image diagram which shows the storage elastic modulus, loss elastic modulus, and Tanδ of the hardened|cured material with a large maximum of the peak of Tanδ.
2 is an image diagram showing the storage elastic modulus, loss elastic modulus, and Tanδ of a cured product having a small maximum value of the peak of Tanδ.

In the curable resin composition of the present invention, the maximum value of Tan δ of the cured product is 0.15 or less in the temperature range of 25 to 300 ° C. If it is such a physical property, stable crack resistance can be obtained even when the temperature of the cured film is exposed from low to high temperature.

In addition, in the present specification, unless otherwise stated, the physical properties of the cured product such as Tanδ, after irradiating ultraviolet light at about 500 mJ/cm ² to the resin layer after drying of the resin composition, 1J / in a UV conveyor equipped with a high-pressure mercury lamp cm ² After further irradiating with an exposure amount, it refers to the physical properties of a cured product having a thickness of 40 μm obtained by heating at 160° C. for 60 minutes to completely cure the resin layer. In addition, an ultraviolet-ray is an electromagnetic wave whose wavelength is 10-400 nm. Tanδ is a value obtained by dividing the loss modulus measured in the dynamic viscoelasticity measurement by the storage modulus, that is, loss tangent (=loss modulus/storage modulus). It is based on the chart figure obtained by measuring from 25 degreeC to 300 degreeC under the conditions of the temperature increase rate of 5 degreeC/min.

In order to obtain a cured product having a small Tanδ (=loss modulus/storage modulus), the loss modulus (viscous component) may be lowered or the storage modulus (elastic component) may be increased, or both, in other words, in the cured product What is necessary is just to make an elastic component more than a viscous component as much as possible.

Although the means for making the maximum value of Tan δ into 0.15 or less is not particularly limited, the average particle diameter is 100 nm to 1 µm, and (A) alkali-soluble resin, (B) thermosetting component, and (C) compound having an ethylenically unsaturated group Using a surface-treated inorganic filler having a reactive group capable of reacting with at least any one, and (B) an epoxy equivalent of 300 g/eq. It is effective to use the following epoxy resins.

(E) When the average particle diameter of the inorganic filler is 1 µm or less, the surface area per volume is large, and it can have many said reactive groups. On the other hand, when an average particle diameter is 100 nm or more, shrinkage|contraction of hardened|cured material is suppressed and crack resistance improves.

Further, (B) as a thermosetting component, the epoxy equivalent is 300 g/eq. Since the crosslinking points with (A) alkali-soluble resin increase by including the following epoxy resins, a crosslinking density goes up, and unreacted (A) alkali-soluble resin etc. can be reduced. From this, the maximum value of Tan δ becomes small, it becomes difficult for hardened|cured material to become hard to change rapidly in the elastic modulus at the time of high temperature of 150 degreeC vicinity, and crack resistance improves more.

Therefore, (E) the inorganic filler and the epoxy equivalent of 300 g / eq. By hardening the composition containing the following epoxy resins, the maximum value of Tanδ of hardened|cured material becomes 0.15 or less in the range of 25-300 degreeC, and stable crack resistance can be acquired. It is preferable that the maximum value of Tan δ is 0.13 or less because crack resistance further improves.

Moreover, Tanδ of hardened|cured material can be made small also by making the compounding quantity of the compound which has (C) an ethylenically unsaturated group small so that it may mention later.

When the maximum value of Tanδ of the cured product is large, when the cured product is exposed to high temperature, the viscous component in the cured product is easy to move and the physical properties change greatly. Since the sea-island viscous component hardly moves, the change in physical properties is small, and the occurrence of cracks is suppressed.

Moreover, although the storage elastic modulus at 150 degreeC of the hardened|cured material of curable resin composition of this invention may be any value if the maximum value of Tanδ of hardened|cured material becomes 0.15 or less, it is preferable that it is 1 GPa or more. More preferably, it is 2 GPa or more. When the storage modulus is 1 GPa or more, the resistance of the cured product to the pressure of water vapor inside the package is improved, and crack resistance and insulation reliability are improved.

In addition, it has been conventionally known that a large change in storage modulus is desirable for absorbing stress in order to obtain crack resistance at high temperature.

However, in the curable resin composition of the present invention, on the contrary, the change rate of the storage elastic modulus is reduced to maintain the toughness even at a high temperature, thereby suppressing the generation of stress and suppressing the occurrence of cracks.

In this invention, it is preferable that the change rate of the storage elastic modulus is small, and it is preferable that the change rate of the storage elastic modulus in 25 degreeC - 150 degreeC is 70 % or less. More preferably, it is within 65 %.

It is preferable that CTE?2 of the hardened|cured material of curable resin composition of this invention is 110 ppm or less, More preferably, it is 100 ppm or less. The smaller the CTEα2, the smaller the change in physical properties even at high temperatures.

It is preferable that curable resin composition of this invention has Tg (glass transition temperature) 160 degreeC or more. More preferably, it is 165 degreeC or more. The higher the Tg, the smaller the change in physical properties at high temperature.

Below, each component of curable resin composition of this invention is demonstrated. In addition, in this specification, (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[(A) alkali-soluble resin]

(A) Alkali-soluble resin is, for example, a resin containing at least one alkali-soluble group among a phenolic hydroxyl group, a thiol group, and a carboxyl group, preferably a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, phenolic The compound which has a hydroxyl group and a carboxyl group, and the compound which has 2 or more of thiol groups are mentioned. (A) As alkali-soluble resin, although carboxyl group-containing resin and phenolic hydroxyl group containing resin can be used, From a viewpoint of reactivity with (B) thermosetting component and (E) inorganic filler, carboxyl group-containing resin is preferable.

Moreover, since the ratio of alkali-soluble groups of alkali-soluble resin increases and the crosslinking density of hardened|cured material increases the one with a smaller weight average molecular weight of (A) alkali-soluble resin, it is preferable. (A) Alkali-soluble resin has a weight average molecular weight in polystyrene conversion at the time of measuring by weight average molecular weight (Mw) gel permeation chromatography (GPC), and it is preferable that it is 10,000 or less.

(A) It is preferable that alkali-soluble resin has an ethylenically unsaturated group in a molecule|numerator other than a carboxyl group from a viewpoint of developability, photocurability, and developability. Moreover, you may use only carboxyl group-containing resin which does not have an ethylenically unsaturated group. As an ethylenically unsaturated group, the thing derived from acrylic acid, methacrylic acid, or those derivatives is preferable.

Specific examples of the carboxyl group-containing resin include compounds listed below (either an oligomer or a polymer).

(1) A carboxyl group containing a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride is added to a hydroxyl group present in a side chain by reacting (meth)acrylic acid with a bifunctional or higher polyfunctional epoxy resin photosensitive resin. Here, it is preferable that a bifunctional or more polyfunctional epoxy resin is solid.

(2) A carboxyl group-containing photosensitive resin in which (meth)acrylic acid is reacted with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of the bifunctional epoxy resin with epichlorohydrin, and dibasic acid anhydride is added to the generated hydroxyl group. Here, it is preferable that a bifunctional epoxy resin is solid.

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

(4) 2 in 1 molecule, such as bisphenol A, bisphenol F, bisphenol S, novolak-type phenol resin, poly-p-hydroxystyrene, a condensate of naphthol and aldehydes, and a condensate of dihydroxynaphthalene and aldehydes A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups 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, and a polybasic acid is obtained in the reaction product A carboxyl group-containing photosensitive resin obtained by reacting an 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 is reacted with an unsaturated group-containing monocarboxylic acid; , A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with the obtained reaction product.

(6) A carboxyl group-containing photosensitive resin obtained by 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.

(7) Polyfunctional oxetane resin as described later is reacted with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid, and a carboxyl group-containing polyester resin obtained by adding a dibasic acid anhydride to a primary hydroxyl group generated .

(8) Carboxyl-group-containing photosensitive resin which added the compound which has a cyclic ether group and (meth)acryloyl group in 1 molecule to carboxyl group-containing resin, such as (1)-(7) mentioned above.

As the carboxyl group-containing resin having an ethylenically unsaturated group (also referred to as a carboxyl group-containing photosensitive resin), it is preferable that the main chain and the side chain ethylenically unsaturated groups derived from a phenol resin or an epoxy resin are separated from each other. In other words, when introducing an ethylenically unsaturated group into a side chain, it is preferable to introduce a chain extension structure so that a certain distance is created between the main chain and the ethylenically unsaturated group. If it is such a structure, since the reactivity of ethylenically unsaturated groups of a side chain improves, it is preferable. As carboxyl group-containing resin which has a chain extension structure and an ethylenically unsaturated group, carboxyl group-containing resin as described in said (3), (4), (5), (8), for example is preferable.

(A) It is preferable that the acid value of alkali-soluble resin is 40-150 mgKOH/g. By making the acid value of carboxyl group-containing resin into 40 mgKOH/g or more, alkali image development becomes favorable. Moreover, drawing of a normal hardened|cured material pattern can be made easy by making an acid value into 150 mgKOH/g or less. More preferably, it is 50-130 mgKOH/g.

(A) The compounding quantity of alkali-soluble resin is 15-60 mass % on the basis of solid content whole quantity of the composition except a solvent, and it is preferable that it is 20-60 mass %. It is 15 mass % or more, Preferably coating-film intensity|strength can be improved by setting it as 20 mass % or more. Moreover, by setting it as 60 mass % or less, a viscosity becomes moderate and workability improves. More preferably, it is 30-50 mass %.

[(B) thermosetting component]

The curable resin composition of the present invention has an epoxy equivalent of 300 g/eq. It contains the following epoxy resins, and more preferably 200 g/eq. is below.

An epoxy resin will not be specifically limited if the said epoxy equivalent is satisfy|filled. Examples of the epoxy resin include epoxidized vegetable oil; bisphenol A epoxy resin; hydroquinone type epoxy resin; bisphenol-type epoxy resin; thioether type epoxy resin; Brominated epoxy resin; novolac-type epoxy resin; Biphenol novolak type epoxy resin; bisphenol F-type epoxy resin; hydrogenated bisphenol A epoxy resin; glycidylamine type epoxy resin; hydantoin-type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; alkylphenol-type epoxy resins (eg, bixylenol-type epoxy resins); Biphenol-type epoxy resin; bisphenol S-type epoxy resin; bisphenol A novolak-type epoxy resin; tetraphenylolethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl xylenoyl ethane resin; naphthalene group-containing epoxy resin; an epoxy resin having a dicyclopentadiene skeleton; triphenylmethane type epoxy resin; an epoxy resin having a silsesquioxane skeleton; glycidyl methacrylate copolymer-based epoxy resin; Copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives; CTBN modified epoxy resin etc. are mentioned. An epoxy resin can be used individually by 1 type or in combination of 2 or more type. Among these, in particular, a novolak-type epoxy resin, a bisphenol-type epoxy resin, a bixylenol-type epoxy resin, a biphenol-type epoxy resin, a biphenol novolac-type epoxy resin, a naphthalene-type epoxy resin, an epoxy resin having a silsesquioxane skeleton, and a tree At least any 1 type of phenylmethane type|mold epoxy resin is preferable.

Epoxy equivalent of 300 g/eq. As commercially available products of the following epoxy resins, EXP7241 (triphenylmethane type epoxy resin) manufactured by DIC, HP6000 (epoxy resin having a naphthalene group), Epiclone N-740 (phenol novolac type epoxy resin), manufactured by Nippon Chemicals Co., Ltd. Epottoto YDC-1312 (hydroquinone type epoxy resin), YSLV-80XY (bisphenol F type epoxy resin), etc. are mentioned.

Since the composition of this invention can make a crosslinking density higher, it is preferable to contain two or more types of polyfunctional epoxy resins as a (B) thermosetting component from a viewpoint of low Tan-delta. In the present specification, "multifunctional" means more than two functionalities. Moreover, it is preferable that the composition of this invention contains (B-1) a bifunctional or more functional epoxy resin whose softening point is 40 degrees C or less as (B) thermosetting component, (B-1) component, and (B-2) ) It is preferable to include a mixture of two or more functional epoxy resins with a softening point exceeding 40°C. (B-1) By including the bifunctional or more than bifunctional epoxy resin whose softening point is 40 degrees C or less, high filling of (E) inorganic filler becomes possible, it becomes low CTE and low Tanδ, and crack resistance improves in a thermal cycle test. Moreover, (B-2) softening point can also raise the glass transition temperature (Tg) of the whole curable resin composition by including the more than bifunctional epoxy resin more than 40 degreeC. As a result, reliability, such as heat resistance, such as PCT resistance, and crack resistance in a thermal cycle test, can be improved more. Here, a softening point means the value measured according to the method of JISK7234.

(B-1) Although a well-known resin may be sufficient as a bifunctional or more than bifunctional epoxy resin whose softening point is 40 degrees C or less, for example, a liquid thing at room temperature is preferable. (B-1) As a commercial item of the bifunctional or more than bifunctional epoxy resin whose softening point is 40 degrees C or less, For example, Epicoat 834, 828 (made by Mitsubishi Chemical Corporation), YD-128 (made by Nippon Tetsu Sumikin Chemical Corporation), 840, 850 ( Bisphenol A type epoxy resin such as DIC), 806, 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Nippon-Sumikin Chemical), 830, 835, N-730A (manufactured by DIC), etc. Bisphenol F type Epoxy resin, a mixture of bisphenol A and bisphenol F such as ZX-1059 (manufactured by Nippon Chemicals Co., Ltd.), YX-8000, 8034 (manufactured by Mitsubishi Chemical) ST-3000 (manufactured by Nippon Chemicals, Ltd.) Hydrogenated bisphenol A type epoxy resin, NOvolak type epoxy resin such as RE-306CA90 manufactured by Nippon Kayaku Corporation, DEN431 and DEN438 manufactured by Dow Chemical Company, and alkylphenol type epoxy resin such as Epiclone HP-820 manufactured by DIC Corporation. there is.

(B-1) The content of the bifunctional or higher epoxy resin having a softening point of 40 ° C. or less, (B-1) The softening point of the bifunctional or higher epoxy resin having a softening point of 40 ° C. or less with respect to 1 equivalent of the alkali-soluble group of the (A) alkali-soluble resin. The epoxy group is preferably in the range from 0.2 to 1.8 equivalents. (B-1) -80-30 degreeC is preferable and, as for the softening point in the bifunctional or more than bifunctional epoxy resin whose softening point is 40 degrees C or less, -70-20 degreeC is more preferable. In the high filling of the inorganic filler (E), which is effective in reducing Tanδ, if a bifunctional or higher epoxy resin having a softening point of 40° C. or less is used, the degree of freedom in the formulation design can be expanded and the adhesive strength can be increased.

(B-2) As a commercial item of the more than bifunctional epoxy resin whose softening point exceeds 40 degreeC, ICTEP-S (softening point: 110 degreeC) manufactured by Nissan Chemical Co., Ltd., TEPIC-H, N870, HP- made by DIC, for example 7200 (softening point: 60°C), HP-4700 (softening point: 90°C), HP-4710 (softening point: 96°C), EXA-7241 (softening point: 70°C), YX-4000 manufactured by Mitsubishi Chemical (softening point: 105) °C), NC-3000L (softening point: 52 °C), NC-7000L (softening point: 86 °C), CER-3000L (softening point: 93 °C), EPPN-502H (softening point: 67 °C), manufactured by Nippon Kayaku Corporation, New Nittetsu Epottoto YSLV-80XY (softening point: 80°C), EPICLON-N660 (softening point: 61 to 69°C) manufactured by Sumikin Chemical, Epottoto YDC-1312 (softening point: 140°C) manufactured by Shin-Nittetsu Sumikin Chemical and the like.

(B-2) 50 degreeC or more is preferable and, as for the softening point in a bifunctional or more than bifunctional epoxy resin in which a softening point exceeds 40 degreeC, 60 degreeC or more is more preferable. In addition, (B-2) Although the upper limit in particular of the softening point in the bifunctional or more than bifunctional epoxy resin whose softening point exceeds 40 degreeC is not restrict|limited, It is about 400 degreeC or less. It is preferable that it is 80 degrees C or less from a viewpoint of workability at the time of forming into a dry film.

(B-1) The mixing ratio of the bifunctional or higher epoxy resin having a softening point of 40 ° C. or less and (B-2) the softening point of the epoxy resin exceeding 40 ° C. Epoxy group (b-1) and (B-2) equivalent ratio (b-1): (b-2) of the epoxy group (b-2) of the bifunctional or higher epoxy resin having a softening point exceeding 40° C. is 3:7 to 9 It is preferably :1, and more preferably 4:6 to 8:2. When the ratio of the epoxy group (b-1) is 3 to 9, both low Tan δ and high Tg can be achieved.

Epoxy equivalent of 300 g/eq. It is especially preferable that the epoxy resin more than trifunctional from a viewpoint of raising a crosslinking density among an epoxy resin as the following epoxy resins is included. The structure of a trifunctional or more than trifunctional epoxy resin is not specifically limited, What is necessary is just an epoxy resin which has three or more epoxy groups. Among them, from the viewpoint of further increasing the crosslinking density, the epoxy equivalent is 200 g/eq. It is more preferable that it is the following trifunctional or more than trifunctional epoxy resin.

As a specific example of the commercial item of the epoxy resin which has a trifunctional or more than trifunctional epoxy group, the trade name "jER-630" (made by Mitsubishi Chemical Corporation) of a trifunctional aminophenol type epoxy resin, the trade name "TEPIC-SP" of a trifunctional triazine skeleton containing epoxy resin (manufactured by Nissan Chemical Industry Co., Ltd.), a brand name of trifunctional aromatic epoxy resin "Tecmore VG3101" (manufactured by PRINTEC), a brand name of tetrafunctional aromatic epoxy resin "GTR-1800" (manufactured by Nippon Kayaku Corporation), modified novolak type epoxy resin of "EPICLON-N740" (manufactured by DIC Corporation), a trade name of dicyclopentadiene type epoxy resin "EPICLON-HP7200H-75M" (manufactured by DIC Corporation), a trade name of cresol novolac type epoxy resin "EPICLON-N660" (manufactured by DIC Corporation) , "jER-152" (manufactured by Mitsubishi Chemical Corporation), a trade name of a phenol novolak-type epoxy resin, "NC3000" (manufactured by Nippon Kayaku Corporation), a trade name of an epoxy resin containing a biphenyl skeleton, "NC3000H" (manufactured by Nippon Kayaku Corporation), " NC3000L" (made by Nippon Kayaku Co., Ltd.), the brand name of a naphthalene type epoxy resin "ESN-175S" (made by Nippon-Sumikin Chemicals), etc. are mentioned.

(B) As a thermosetting component, the epoxy resin which has a silsesquioxane skeleton among the said epoxy resins can be used more suitably. By mix|blending the epoxy resin which has a silsesquioxane skeleton, the ratio of the inorganic component of a composition increases, and a viscous component decreases. Thereby, the maximum value of Tan δ becomes small, and it becomes difficult for hardened|cured material to cure shrinkage at the time of high temperature. As an epoxy resin having a silsesquioxane skeleton, a network-type polymer or polyhedral cluster having _a structure of _{(RSiO 1.5 )} n obtained by hydrolyzing silsesquioxane, that is, trifunctional silane, a group containing an epoxy group It will not specifically limit if it is a compound which has. Each silicon of silsesquioxane has an average of 1.5 oxygen atoms and 1 hydrocarbon group bonded to it.

It is preferable that the epoxy resin which has silsesquioxane frame|skeleton has silsesquioxane frame|skeleton represented by following General formula (1).

(Wherein, R ¹ to R ⁴ are each independently a group or an organic group having a SiO bond, and at least one of R ¹ to R ⁴ is a group having an epoxy group.) Here, the organic group is a group containing a carbon atom. say

The structure of the said silsesquioxane is not specifically limited, Silsesquioxane of well-known and usual structures, such as a random structure, a ladder structure, a complete cage structure, and an incomplete cage structure, can be used.

The group having a SiO bond that R ¹ to R ⁴ can take is not particularly limited, and examples include a group having an SiO bond and an aliphatic skeleton, a group having an SiO bond and an aromatic skeleton, and a group having a SiO bond and a hetero atom. And it is preferable to become in the range of the equivalent of the said thermosetting functional group (epoxy group).

The organic group containing a carbon atom that R ¹ to R ⁴ can take 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 a group having a hetero atom. Preferably it is a C1-C30 organic group, and it is preferable to become in the range of the equivalent of the said thermosetting functional group (epoxy group).

At least one of R ¹ to R ⁴ is a group having an epoxy group, and the group having an epoxy group is not particularly limited, and the group or organic group having a SiO bond may have an epoxy group.

(B) The compounding quantity of a thermosetting component is 1-100 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, 10-80 mass parts is preferable, and 20-60 mass parts is more preferable. (B) Crack resistance and insulation reliability improve that the compounding quantity of a thermosetting component is 1 mass part or more, and storage stability improves that it is 100 mass parts or less.

The curable resin composition of the present invention has an epoxy equivalent of 300 g/eq. You may contain well-known thermosetting components other than the following epoxy resins. For example, amino resins such as melamine resins, benzoguanamine resins, melamine derivatives and benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy resins having an epoxy equivalent of more than 300 g/eq. Well-known compounds, such as an oxetane compound, episulfide resin, bismaleimide, and carbodiimide resin, can be used. Particularly preferred are compounds having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter, abbreviated as cyclic (thio)ether groups) in the molecule. The compound having a plurality of cyclic (thio)ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio)ether groups in the molecule, for example, a compound having a plurality of epoxy groups in the molecule, that is, and a functional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, ie, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, ie, a polyfunctional episulfide resin, and the like.

[(C) Compound having an ethylenically unsaturated group]

Curable resin composition of this invention contains the compound which has (C) ethylenically unsaturated group. (C) As a compound which has an ethylenically unsaturated group, the compound which has 1 or more ethylenically unsaturated group in a molecule|numerator is used preferably. As a compound which has an ethylenically unsaturated group, the photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc. which are a well-known and usual compound which has an ethylenically unsaturated group can be used. In addition, (A) alkali-soluble resin and (E) surface-treated inorganic filler which have an ethylenically unsaturated group shall not be contained in the compound which has (C) ethylenically unsaturated group here.

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

As a photopolymerizable vinyl monomer, a well-known and usual thing, For example, Styrene derivatives, such as styrene, chlorostyrene, (alpha)-methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate, or vinyl benzoate; Vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl vinyl ethers such as ether and triethylene glycol monomethyl vinyl ether; (acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, N-butoxymethylacrylamide, etc.) meth)acrylamides; allyl compounds such as triallyl isocyanurate, diallyl phthalate, and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isoboronyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) ) esters of (meth)acrylic acid such as acrylates; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and pentaerythritol tri(meth)acrylate; Alkoxyalkylene glycol mono(meth)acrylates, such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Ethylene glycol di(meth)acrylate, butanediol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , pentaerythritol tetra(meth)acrylate, and alkylene polyol poly(meth)acrylates such as dipentaerythritol hexa(meth)acrylate; Polyoxyalkylene glycol poly(es) such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane tri(meth)acrylate meth) acrylates; poly(meth)acrylates such as hydroxypivalic acid neopentyl glycol ester di(meth)acrylate; Isocyanurate-type poly(meth)acrylates, such as tris[(meth)acryloxyethyl] isocyanurate, etc. are mentioned. These can be used individually or in combination of 2 or more types according to a required characteristic.

(C) It is preferable that the compounding quantity of the compound which has an ethylenically unsaturated group is less than 20 mass parts with respect to 100 mass parts of (A) alkali-soluble resin, More preferably, it is 5-18 mass parts, More preferably, it is 10-15 mass parts. is the mass part. (C) By reducing the compounding quantity of the compound which has an ethylenically unsaturated group, the compound which has unreacted ethylenically unsaturated group in hardened|cured material can be reduced, and loss elastic modulus (viscous component) can be reduced.

[(D) Photoinitiator]

(D) As a photoinitiator, if it is a well-known photoinitiator as a photoinitiator and a photoradical generator, any can be used.

As a photoinitiator, For example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6- Dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-( 2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4, bisacylphosphine oxides such as 6-trimethylbenzoyl)-phenylphosphine oxide (IRGACURE819 manufactured by BASF Japan); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine methyl ester, 2-methylbenzoyldiphenylphosphine oxide, P monoacylphosphine oxides such as valoylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IRGACURE TPO manufactured by BASF Japan); 1-Hydroxy-cyclohexylphenylketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1 -{4-[4-(2-Hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropane- hydroxyacetophenones such as 1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2- acetophenones such as (dimethylamino)-2-[(4-methylphenyl)methyl)-1-[4-(4-morpholinyl)phenyl]-1-butanone and N,N-dimethylaminoacetophenone; Thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-chlorothioxanthone, 2,4-di thioxanthone such as isopropyl thioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, and p-dimethylbenzoic acid ethyl ester; 1,2-Octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbox oxime esters such as bazol-3-yl]-,1-(O-acetyloxime); Bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)- titanocenes such as bis[2,6-difluoro-3-(2-(1-phyll-1-yl)ethyl)phenyl]titanium; Phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, etc. are mentioned. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, monoacyl phosphine oxides and oxime esters are preferable, and highly sensitive oxime esters are most preferable. As oxime esters, those having one or two or more oxime ester groups are preferable, for example, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] -,1-(O-acetyloxime) is more preferable.

It is preferable that the compounding quantity of a photoinitiator is 0.5-20 mass parts with respect to 100 mass parts of (A) alkali-soluble resin. When it is 0.5 mass part or more, surface hardenability becomes favorable, and when it is 20 mass parts or less, it is hard to generate|occur|produce halation, and favorable resolution is acquired.

[(E) Surface-treated inorganic filler]

The curable resin composition of the present invention has an average particle diameter of 100 nm to 1 µm and has a reactive group capable of reacting with at least one of (A) alkali-soluble resin, (B) thermosetting component, and (C) compound having an ethylenically unsaturated group. (E) contains a surface-treated inorganic filler.

The inorganic filler is not particularly limited, and known and conventional fillers such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic mica, aluminum hydroxide , barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, inorganic fillers such as zinc oxide can be used. Among these, silica is preferable, and since it has a small surface area and stress is dispersed throughout, it is difficult to become a crack origin, and spherical silica is more preferable from the viewpoint of excellent resolution.

(E) Examples of the reactive group of the surface-treated inorganic filler include a (meth)acryloyl group, a vinyl group, a cyclic (thio)ether group, an acidic group, and a basic group.

Examples of the cyclic (thio)ether group include an epoxy group, an oxetanyl group, and an episulfide group.

Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a thiol group, a sulfone group, and a phosphoric acid group.

As a basic group, an amino group, an amide group, an ammonium group, etc. are mentioned, for example.

(E) The reactive group of the surface-treated inorganic filler is preferably any one of a (meth)acryloyl group, a vinyl group, and a cyclic (thio)ether group. (E) If the reactive group of the surface-treated inorganic filler is a cyclic (thio)ether group, (A) it is excellent in reactivity with an alkali-soluble resin, and if it is a (meth)acryloyl group or a vinyl group, (A) the ethylenic property of the alkali-soluble resin It has excellent reactivity with unsaturated groups and the like.

The method of introducing the reactive group into the inorganic filler is not particularly limited, and may be introduced using a known and conventional method, and the surface of the inorganic filler is treated with a surface treatment agent having the reactive group, for example, a coupling agent having the reactive group. Do it.

As surface treatment of an inorganic filler, the surface treatment by a coupling agent is preferable. As a coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. can be used. Especially, a silane coupling agent is preferable.

As the silane coupling agent capable of introducing the reactive group into the inorganic filler, a silane coupling agent having a vinyl group, a silane coupling agent having a methacryl group, a silane coupling agent having an acryl group, a silane coupling agent having an epoxy group, a silane coupling agent having a carboxyl group, etc. Among these, the silane coupling agent which has at least any one of a (meth)acryl group and a vinyl group is preferable.

(E) The surface-treated inorganic filler may be blended with the curable resin composition of the present invention in a surface-treated state, and the inorganic filler may be surface-treated in the composition by blending the surface-untreated inorganic filler and the surface treating agent, respectively, but in advance It is preferable to mix|blend the surface-treated inorganic filler. By mix|blending the inorganic filler surface-treated in advance, the fall of the crack resistance etc. by the surface treating agent which is not consumed in the surface treatment which may remain|survive when each mix|blended can be prevented. In the case of surface treatment in advance, it is preferable to blend a pre-dispersion in which an inorganic filler is pre-dispersed in a solvent or a resin component, the surface-treated inorganic filler is pre-dispersed in a solvent, and the pre-dispersion is blended into the composition, or the surface is untreated It is more preferable to mix|blend this pre-dispersion liquid with a composition after surface-treating sufficiently when pre-dispersing the used inorganic filler in a solvent.

(E) The average particle diameter of the surface-treated inorganic filler is preferably 100 to 800 nm, more preferably 100 to 700 nm, still more preferably 200 to 700 nm. In addition, in this specification, (E) the average particle diameter of the surface-treated inorganic filler is the average particle diameter (D50) including the particle diameter of not only the particle diameter of a primary particle but the secondary particle (aggregate). An average particle diameter can be calculated|required with the laser diffraction type particle diameter distribution measuring apparatus. As a measuring apparatus by a laser diffraction method, the Nikkiso company nanotrac wave etc. are mentioned.

(E) The more the compounding quantity of the surface-treated inorganic filler is, the more the storage elastic modulus increases, the Tanδ becomes small, and the cured product becomes difficult to expand. It is preferable that it is 35 mass % or more per the whole quantity of. More preferably, it is 38-80 mass %.

(thermosetting catalyst)

It is preferable that curable resin composition of this invention contains a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 4-phenylimidazole. imidazole derivatives such as , 1-cyanoethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; Phosphorus compounds, such as a triphenylphosphine, etc. are mentioned. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-tri Azine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid S-triazine derivatives, such as adducts, can also be used, Preferably, the compound which functions also as these adhesion-imparting agents is used together with a thermosetting catalyst.

Preferably the compounding quantity of a thermosetting catalyst is 0.05-20 mass parts with respect to 100 mass parts of (B) thermosetting components, More preferably, it is 0.1-15 mass parts.

(hardener)

The curable resin composition of this invention may contain a hardening|curing agent. Examples of the curing agent include phenol resins, polycarboxylic acids and acid anhydrides thereof, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. A hardening|curing agent can be used individually by 1 type or in combination of 2 or more type.

(coloring agent)

The colorant may be contained in the curable resin composition of this invention. As a coloring agent, well-known coloring agents, such as red, blue, green, yellow, black, and white, can be used, Any of a pigment, dye, and a pigment|dye may be sufficient. However, it is preferable not to contain a halogen from a viewpoint of environmental load reduction and an influence on a human body.

Although there is no restriction|limiting in particular of the addition amount of a coloring agent, Preferably it is 10 mass parts or less with respect to 100 mass parts of (A) alkali-soluble resin, Especially preferably, the ratio of 0.1-7 mass parts is sufficient.

(organic solvent)

The curable resin composition of this invention can be made to contain the organic solvent for the purpose of manufacture of a composition, viscosity adjustment at the time of apply|coating to a board|substrate or a carrier film, etc. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether glycol ethers such as acetate and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; A well-known and usual organic solvent, such as petroleum solvents, such as petroleum ether, petroleum naphtha, and solvent naphtha, can be used. These organic solvents can be used individually or in combination of 2 or more types.

(Other optional ingredients)

In addition, you may mix|blend with the curable resin composition of this invention other well-known and usual additives in the field|area of an electronic material. Examples of the other additives include a thermal polymerization inhibitor, a UV absorber, a silane coupling agent, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/mildew inhibitor, an antifoaming agent, a leveling agent, a thickener, an adhesion imparting agent, a thixotropic imparting agent, and a photoinitiator. An auxiliary agent, a sensitizer, a thermoplastic resin, an organic filler, a mold release agent, a surface treatment agent, a dispersing agent, a dispersion auxiliary agent, a surface modifier, a stabilizer, a fluorescent substance, the block copolymer of AB type or ABA type, etc. are mentioned.

The curable resin composition of the present invention may be used as a dry film, or may be used in a liquid state. When using as a liquid, one-component or two-component or more may be sufficient.

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

A plastic film is used as a carrier film, For example, polyester films, such as a polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, etc. can be used. Although there is no restriction|limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. More preferably, it is the range of 15-130 micrometers.

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

Moreover, in this invention, you may form a resin layer by apply|coating and drying the curable resin composition of this invention on the said cover film, and laminating|stacking a carrier film on the surface. That is, when manufacturing a dry film in this invention, you may use any of a carrier film and a cover film as a film which apply|coats curable resin composition of this invention.

The printed wiring board of this invention has the hardened|cured material obtained from the resin layer of curable resin composition of this invention or a dry film. As a manufacturing method of the printed wiring board of this invention, for example, the curable resin composition of this invention is adjusted to the viscosity suitable for a coating method using the said organic solvent, and the dip coating method, the flow coating method, the roll coating method on a base material. , a bar coater method, screen printing method, curtain coating method, etc., followed by volatilization drying (temporary drying) of the organic solvent contained in the composition at a temperature of 60 to 100 ° C. to form a dry to touch resin layer do. Moreover, in the case of a dry film, after bonding on a base material so that a resin layer may contact a base material with a laminator etc., a resin layer is formed on a base material by peeling a carrier film.

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

The volatilization drying performed after the curable resin composition of the present invention is applied is a hot air circulation drying furnace, an IR furnace, a hot plate, a convection oven, etc. A method of making contact and a method of spraying from a nozzle to a support) can be used.

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

As the exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc. are mounted, and any device that irradiates ultraviolet rays in the range of 350 to 450 nm is sufficient, and it is also a direct drawing device (For example, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer) can also be used. As a lamp light source or a laser light source of a straight drawing machine, what is necessary is just to exist in the range of 350-450 nm of maximum wavelength. Although the exposure amount for image formation varies depending on the film thickness and the like, it can be generally within the range of 10 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .

The developing method can be carried out by a dipping method, a shower method, a spraying method, a brush method, or the like. As the developer, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines is used. can

Curable resin composition of this invention is used suitably in order to form a cured film on a printed wiring board, In order to use in order to form a permanent film more suitably, More suitably, in order to form a soldering resist, an interlayer insulating layer, and a coverlay. used Moreover, it is suitable for formation of the printed wiring board provided with the wiring pattern of the fine pitch which high reliability is requested|required, for example, a package board|substrate, especially the permanent film (especially soldering resist) for FC-BGA. In particular, according to the curable resin composition of the present invention, a cured product excellent in crack resistance when a high-temperature load is applied can be obtained, and thus it is suitable for applications exposed to a high temperature state such as in-vehicle applications.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to the following examples. In addition, in the following, "part" and "%" are both based on mass unless otherwise indicated.

[Synthesis of alkali-soluble resin A-1]

119.4 parts of novolak-type cresol resin (trade name "Shonol CRG951", manufactured by Showa Kobunshi Co., Ltd., OH equivalent: 119.4), 1.19 parts of potassium hydroxide, in an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device and a stirring device and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Then, 63.8 parts of propylene oxide were dripped gradually, and it was made to react at 125-132 degreeC, and 0-4.8 kg/cm< ² > for 16 hours. Thereafter, the mixture was cooled to room temperature and mixed with 1.56 parts of 89% phosphoric acid to the reaction solution to neutralize potassium hydroxide, and a novolak-type cresol having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.) A propylene oxide reaction solution of the resin was obtained. As for this, 1.08 mol of propylene oxide was added on average per equivalent of phenolic hydroxyl group.

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

[Synthesis of alkali-soluble resin A-2]

Diethylene glycol monoethyl ether acetate 700 g to orthocresol novolak epoxy resin (DIC Corporation, EPICLON N-695, softening point 95 ° C, epoxy equivalent 214, average number of reactive groups 7.6) 1070 g (the number of glycidyl groups (total number of aromatic rings)) : 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were added, and the mixture was heated and stirred at 100° C. to uniformly dissolve.

Next, 4.3 g of triphenylphosphine was added, and after heating at 110° C. and reacting for 2 hours, 1.6 g of triphenylphosphine was further added, and the temperature was raised to 120° C. and reaction was further performed for 12 hours. 562 g of aromatic hydrocarbons (Sorvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added to the obtained reaction liquid, and reaction was performed at 110 degreeC for 4 hours. Furthermore, 142.0 g (1.0 mol) of glycidyl methacrylate was thrown into the obtained reaction liquid, reaction was performed at 115 degreeC for 4 hours, and the carboxyl group-containing photosensitive resin solution (A-2) was obtained.

Thus, 65% of solid content of the obtained photosensitive resin solution (A-2) and the acid value of solid content were 87 mgKOH/g.

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

90.0 parts of γ-glycidoxypropyltrimethoxysilane, 3.0 parts of phenyltrimethoxysilane, 2.0 parts of methyltrimethoxysilane, and 93 parts of methylisobutylketone were put into a reaction vessel, and the temperature was raised to 80°C. After heating up, 21.6 parts of 0.1 weight% potassium hydroxide aqueous solution was dripped continuously over 30 minutes. After completion of the dropwise addition, the reaction was performed at 80°C for 5 hours while removing the produced methanol. After completion of the reaction, washing with water was repeated until the washing solution became neutral. Then, 69 parts of epoxy resins which have silsesquioxane frame|skeleton were obtained by removing a solvent under reduced pressure. The epoxy equivalent of the obtained epoxy resin was 176 g/eq., and the weight average molecular weight was 2200.

[Adjustment of surface-treated inorganic filler (silica) E-1]

70 g of spherical silica (SFP-30M manufactured by Denka Corporation, average particle diameter: 600 nm), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having a methacryl group (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) ) 2 g was uniformly dispersed to obtain a silica solvent dispersion product E-1.

[Adjustment of surface-treated inorganic filler (silica) E-2]

70 g of spherical silica (SFP-20M manufactured by Denka Corporation, average particle diameter: 300 nm), 28 g of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a silane coupling agent having an epoxy group (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) 4 g was uniformly dispersed, and silica solvent dispersion product E-2 was obtained.

[Examples 1 to 17, Comparative Examples 1 to 5]

The above-described resin solution (varnish) is blended with the various components shown in Tables 1 to 3 in the ratios (parts by mass) shown in Tables 1 to 3, premixed with a stirrer, and then kneaded with a triaxial roll mill to curable resin A composition was prepared.

<Production of dry film>

To the curable resin composition obtained as mentioned above, 300 g of methyl ethyl ketone was added and diluted, and it stirred for 15 minutes with a stirrer, and obtained the coating liquid. The coating solution was coated on a polyethylene terephthalate film (Envet PTH-25 manufactured by Unitica Co., Ltd.) having a thickness of 38 µm with an arithmetic surface roughness Ra of 150 nm, dried at a temperature of usually 80 ° C. for 15 minutes, and photosensitive water having a thickness of 20 µm A stratum was formed. Next, an 18-micrometer-thick polypropylene film (OPP-FOA made by Futamura Corporation) was bonded on the photosensitive resin layer, and the photosensitive dry film was produced.

<Production of cured coating film>

The polyethylene film is peeled from the photosensitive dry film obtained as described above on the low-profile copper foil, the photosensitive resin layer of the photosensitive dry film is bonded to the copper foil surface side, and then a vacuum laminator (MVLP manufactured by Meiki Seisakusho) -500) was used for heat lamination under the conditions of a pressure degree of 0.8 MPa, 70° C., 1 minute, and a degree of vacuum: 133.3 Pa, so that the substrate and the photosensitive resin layer were brought into close contact.

Next, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), exposure from the photosensitive dry film (exposure amount: 400 to 600 mJ/cm ² ), the polyethylene terephthalate film is peeled from the photosensitive dry film, The resin layer was exposed. Thereafter, using a 1 wt% Na ₂ CO ₃ aqueous solution, development was performed for 60 seconds at 30° C. and a spray pressure of 2 kg/cm ² , thereby forming a resin layer having a predetermined resist pattern. Then, after irradiating the resin layer with an exposure amount of 1J/cm ² in a UV conveyor furnace equipped with a high-pressure mercury lamp, the resin layer was completely cured by heating at 160° C. for 60 minutes to prepare a cured coating film.

<Evaluation of Tanδ, Tg, and storage modulus>

The cured coating film obtained as described above was peeled from the copper foil, the sample was cut out so that a measurement size (size of 5 mm x 10 mm) was obtained, and the temperature was raised from 25 ° C. to 300 ° C. with DMS6100 manufactured by Hitachi Hi-tech Co., Ltd. 5 ° C./min, frequency 1 Hz, Measurements were made in the tensile sinusoidal mode.

Tanδ takes the maximum value in the temperature measurement region, the temperature at this time is Tg, and the storage elastic modulus (E') took data of 25°C (E'1) and 150°C (E'2).

The rate of change of the storage elastic modulus (E') was obtained by calculating from (E'1-E'2)/E'1 using the storage elastic modulus of the said two points|pieces.

<Evaluation of CTE>

The cured coating film obtained as mentioned above was peeled from copper foil, the sample was cut out so that the measurement size (size of 3 mm x 10 mm) might be obtained, and CTE was measured with TMA6100 by a Hitachi High-tech company. The measurement conditions were repeated twice of heating the sample from room temperature at a temperature increase rate of 10°C/min with a test load of 5 g, to obtain a coefficient of linear expansion (CTE(α2)) equal to or greater than Tg in the second time.

<Crack resistance (TCT resistance)>

The surface of the circuit-formed substrate (50 mm × 50 mm × 0.4 mmt) having a bump pitch of 250 μm connected to C4 was chemically polished, and the polyethylene film was peeled from the photosensitive dry film obtained as described above, and the photosensitive dry film was applied to the surface of the polished side. of the photosensitive resin layer, and then, using a vacuum laminator (MVLP-500 manufactured by Meiki Seisakusho), heat lamination under the conditions of pressure degree: 0.8 MPa, 70 ° C., 1 minute, vacuum degree: 133.3 Pa, and the substrate and photosensitivity The resin layer was adhered. Then, using an exposure apparatus equipped with a high-pressure mercury lamp (short arc lamp), exposure was performed from the photosensitive dry film through an exposure mask having a negative pattern of 70 μm in diameter, and then the polyethylene terephthalate film was peeled from the photosensitive dry film. , the photosensitive resin layer was exposed. Thereafter, using a 1 wt% Na ₂ CO ₃ aqueous solution, development was performed for 60 seconds at 30° C. and a spray pressure of 2 kg/cm ² , thereby forming a resin layer having a predetermined resist pattern. Then, after irradiating the resin layer with an exposure dose of 1J/cm ² in a UV conveyor furnace equipped with a high-pressure mercury lamp, heating at 160° C. for 60 minutes to completely harden the resin layer to form a cured film, TST with a cured film installed on the substrate An evaluation board was produced.

Next, after mounting a 20 mm square chip by the C4 method, heat treatment at 125° C. for 24 hours as preconditioning, humidification treatment at 60° C. humidity 60% for 48 hours, and reflow 260° C. 3 times did. The obtained board|substrate was put into the cooling-heat cycle machine in which the temperature cycle between -65 degreeC and 175 degreeC is performed, and TCT (Thermal Cycle Test) was performed. And the appearance at the time of 300 cycles, at the time of 600 cycles, and 800 cycles was observed.

◎◎: No abnormality at 1000 cycles or more.

(double-circle): No abnormality in 800 cycles or more.

○: Cracks occurred at 800 cycles.

(triangle|delta): Crack generation|occurrence|production at 600 cycles.

×: Cracks occurred at 300 cycles.

*1: carboxyl group-containing resin A-1 synthesized above (alkali-soluble group equivalent: 701.3 g/eq.)

*2: carboxyl group-containing resin A-2 synthesized above (alkali-soluble group equivalent: 579 g/eq.)

*3: PCR-1170H (a carboxyl group-containing resin starting from a phenol novolak-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. (Alkali-soluble group equivalent: 656 g/eq.)

*4: Epoxy resin B-1 having a silsesquioxane skeleton synthesized above (epoxy equivalent: 176 g/eq., bifunctional, softening point: -50°C)

*5: DIC Corporation Epiclone N-740 (phenol novolak type epoxy resin, epoxy equivalent: 180 g/eq., trifunctional, softening point: 30°C)

*6: DIC Corporation Epiclone HP-7200H (epoxy resin having a dicyclopentadiene skeleton, epoxy equivalent: 280 g/eq., bifunctional, softening point: 75 to 90°C)

*7: DIC Corporation Epiclone HP-820 (alkylphenol type epoxy resin, epoxy equivalent: 225 g/eq., bifunctional, liquid)

*8: Epottoto YDC-1312 manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd. (hydroquinone type epoxy resin, epoxy equivalent: 178 g/eq., bifunctional, softening point: 140°C)

*9: Epottoto YSLV-80XY manufactured by Shin-Nittetsu Sumikin Chemical Co., Ltd. (bisphenol F-type epoxy resin, epoxy equivalent: 195 g/eq., bifunctional, softening point: 80°C)

*10: Epiclon 152 manufactured by DIC Corporation (tetrabromobisphenol A type epoxy resin, epoxy equivalent: 360 g/eq., bifunctional, softening point: 56 to 66° C.)

*11: jER1001 manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin, epoxy equivalent: 475 g/eq., bifunctional, softening point: 64°C)

*12: Shikoku Chemical Co., Ltd. 2PHZ (2-phenyl-4,5-dihydroxymethylimidazole)

*13: dicyandiamide

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

*15: Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF Japan

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

*17: Surface-treated silica solvent dispersion E-1 (silica having a methacryl group as a reactive group) adjusted above (silica content 70 mass % (solid content)) (average particle size 600 nm) (Numbers in the table indicate the solid content indicate)

*18: Surface-treated silica solvent dispersion E-2 (silica having an epoxy group as a reactive group) adjusted above (silica content 68.6 mass % (solid content)) (average particle size 300 nm) (Numbers in the table indicate the solid content )

*19: Admanano YA050C-SV2 manufactured by Admatex Corporation (silica having a vinyl group as a reactive group) (average particle diameter of 50 nm)

*20: Admafine SO-C2 (spherical silica, average particle size 0.5 μm) manufactured by Admatex Co., Ltd.

*21: Admafine SO-C5 manufactured by Admatex Corporation (spherical silica, average particle diameter 1.5 µm)

*22: Nippon Kayaku Co., Ltd. NC-3000L (biphenylene type epoxy resin, epoxy equivalent: 273 g/eq., bifunctional, softening point: 52°C)

*23: DIC Corporation EXA-7241 (triphenylmethane type epoxy resin, epoxy equivalent: 168 g/eq., trifunctional, softening point: 70 ° C.),

*24: EPICLON-N660 manufactured by DIC (cresol novolak type epoxy resin, epoxy equivalent: 210 g/eq., bifunctional, softening point: 61 to 69°C)

From the result shown in the said table|surface, it turned out that the hardened|cured material of the curable resin composition of Examples 1-17 of this invention is excellent in crack resistance. On the other hand, in the hardened|cured material of the curable resin composition of Comparative Examples 1-5, the maximum value of Tan δ exceeded 0.15, and crack resistance was not acquired.

Claims (12)

(A) alkali-soluble resin,
(B) a thermosetting component;
(C) a compound having an ethylenically unsaturated group;
(D) a photopolymerization initiator, and
(E) a resin composition containing a surface-treated inorganic filler,
The surface-treated inorganic filler (E) has an average particle diameter of 100 nm to 1 µm, and at least any one of (A) alkali-soluble resin, (B) thermosetting component, and (C) compound having an ethylenically unsaturated group having a reactive group capable of reacting with a species,
As the (B) thermosetting component, an epoxy equivalent of 300 g/eq. Containing the following epoxy resins,
The (A) alkali-soluble resin includes the carboxyl group-containing resin described in the following (3), (4), (5) or (8),
(3) An epoxy compound having two or more epoxy groups in one molecule, an alcoholic hydroxyl group in a reaction product obtained by reacting a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule with an unsaturated group-containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride with
(4) Carboxyl group-containing photosensitivity obtained by reacting a reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide with a monocarboxylic acid containing an unsaturated group, and reacting a polybasic acid anhydride with the reaction product obtained profit,
(5) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with a cyclic carbonate compound is reacted with an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride is reacted with the reaction product obtained. A carboxyl group-containing photosensitive resin;
(8) A carboxyl group-containing photosensitive resin obtained by adding a compound having a cyclic ether group and a (meth)acryloyl group in one molecule to the carboxyl group-containing resin of (3), (4) or (5) above;
The (C) compound having an ethylenically unsaturated group does not contain the (A) alkali-soluble resin having an ethylenically unsaturated group and the (E) surface-treated inorganic filler,
In the cured product having a thickness of 40 μm obtained from the resin composition, the maximum value of Tanδ is 0.15 or less when dynamic viscoelasticity is measured from 25° C. to 300° C. under the conditions of a frequency of 1 Hz and a temperature increase rate of 5° C./min. Curable resin composition. The carboxyl group-containing resin according to claim 1, wherein the unsaturated group-containing monocarboxylic acid is (meth)acrylic acid, and the polybasic acid anhydride is maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride or adipic anhydride,
In the carboxyl group-containing resin according to the above (4), the compound having two or more phenolic hydroxyl groups in one molecule is bisphenol A, bisphenol F, bisphenol S, novolak-type phenol resin, poly-p-hydroxystyrene, naphthol a condensate of an aldehyde or a condensate of dihydroxynaphthalene and an aldehyde, wherein the alkylene oxide is ethylene oxide or propylene oxide, and the monocarboxylic acid containing an unsaturated group is (meth)acrylic acid;
The carboxyl group-containing resin according to (5) above, wherein the cyclic carbonate compound is ethylene carbonate or propylene carbonate. The method of claim 1, wherein the epoxy equivalent of 300 g/eq. As the following epoxy resins, (B-1) a bifunctional or more functional epoxy resin having a softening point of 40° C. or less, and (B-2) a bifunctional or more functional epoxy resin having a softening point of 40° C. or less. A curable resin composition comprising: The curable resin composition according to claim 1, wherein the amount of the compound having an ethylenically unsaturated group (C) is less than 20 parts by mass based on 100 parts by mass of the alkali-soluble resin (A). The curable resin composition according to claim 1, wherein the (E) surface-treated inorganic filler is blended in an amount of 35 mass % or more in the solid content of the curable resin composition. The storage modulus of claim 1, wherein the cured product has a storage elastic modulus of 1 GPa or more, and a storage modulus of 1 GPa or more at 150° C. The curable resin composition characterized in that the rate of change of the storage elastic modulus up to 150°C is within 70%. The curable resin composition according to claim 1, wherein CTEα2 of the cured product is 110 ppm or less. The curable resin composition according to claim 1, wherein the cured product has a Tg of 160°C or higher. The curable resin composition according to claim 1, which is used for forming a solder resist. It has a resin layer obtained by apply|coating and drying the curable resin composition of Claim 1 to a film, The dry film characterized by the above-mentioned. Hardened|cured material obtained by hardening|curing the resin layer of the curable resin composition in any one of Claims 1-9, or the dry film of Claim 10, The hardened|cured material characterized by the above-mentioned. It has the hardened|cured material of Claim 11, The printed wiring board characterized by the above-mentioned.

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