TW202204435A - 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 exhibits excellent crack resistance when a high temperature load is applied thereto; and the like. A curable resin composition which contains (A) an alkali-soluble resin, (B) a thermosetting component, (C) a compound having an ethylenically unsaturated group, (D) a photopolymerization initiator and (E) a surface-treated inorganic filler, and which is characterized in that: the inorganic filler (E) has an average particle diameter of 100 nm to 1 [mu]m, and comprises a reactive group that is able to react with at least one of the alkali-soluble resin (A), the thermosetting component (B) and the compound (C) having an ethylenically unsaturated group; an epoxy resin having an epoxy equivalent weight of300 g/eq. or less is contained as the thermosetting component (B); and with respect to a cured product obtained from the resin composition and having a thickness of 40 [mu]m, the maximum value of Tan[delta] as determined by dynamic viscoelasticity measurement performed at a frequency of 1 Hz at a heating rate of 5 DEG C/min from 25 DEG C to 300 DEG C is 0.15 or less.

Description

Curable resin composition, dry film, cured product, and printed wiring board

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

In recent years, with the rapid progress of semiconductor parts, electronic devices tend to be thinner, thinner, smaller, higher performance, and more functional. Following this trend, miniaturization and multi-pinning of semiconductor packages have been put into practical use.

Specifically, IC packages called BGA (Ball Grid Array), CSP (Chip Scale Package), etc. are used instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), and the like. In addition, in recent years, FC-BGA (Flip chip.Ball grid array) has also been used as an IC package with a higher density. In such a printed wiring board (also called a package substrate) used in IC packaging, the pitch of SRO (Solder Resist Opening) is narrowed and formed close to each other, so the solder photoresist formed between the SROs becomes relatively small. Thin and thin, and prone to cracking.

In the future, on the other side of the progress of the thinning of the solder photoresist, the heat generation of the mounted parts tends to increase, so it is necessary to further increase the temperature at high temperatures. crack resistance. In particular, the parts used in vehicles have high current density and are prone to high temperature, so the premise is that they should be used in an environment where cracks are more likely to occur.

Conventionally, as a method for improving the crack resistance, for example, a photocurable resin composition comprising an epoxy resin containing an acid-modified vinyl group, an elastomer, a photopolymerization initiator, a diluent, and a hardener has been disclosed (for example, patent documents 1). This patent document 1 discloses that crack resistance is improved by an elastic body.

However, only by the above-mentioned means, when crack resistance is further required in a high temperature state in the future, satisfactory results cannot be obtained.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 11-240930

Therefore, an object of the present invention is to provide a curable resin composition, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and a printed wiring having the cured product The curable resin composition can obtain a cured product excellent in crack resistance under high temperature load.

By applying various applications to the solder photoresist used in IC packaging force, and these stresses will accumulate, and the unbearable stress will be released into cracks.

The stress mainly includes (1) the stress generated by the thermal linear expansion (CTE) difference between the solder photoresist and the surrounding components (copper, substrate, etc.), (2) the gas generated by the thermal history during packaging (solder photoresist and (3) The stress (skew) caused by the cross-linking reaction in the solder photoresist caused by the thermal history after mounting. Conventionally, in order to suppress cracking, the method of blending an elastomer or the like in the solder photoresist to relax the stress, or the method of increasing the glass transition temperature (Tg) and lowering the CTE of the solder photoresist, has caused the above-mentioned (1). stress is effective.

However, in recent years, IC packages for automotive applications are exposed to high temperature environments, so the stress caused by (2) or (3) will increase due to the influence of the temperature environment, thermal history, and components used, and since the stress is Since it is infinite, it is sometimes impossible to completely prevent stress from being generated in a simple stress relaxation and in those with high Tg and low CTE.

Here, the inventors have found that, in addition to the means of reducing the thermal expansion coefficient after curing, for solder photoresists whose thermal expansion coefficient and elastic modulus change due to heat, there is also a method for reducing the elastic modulus above Tg after curing. Characteristically, it is necessary to evaluate the viscoelasticity of DMA considering the force (viscosity) proportional to the displacement velocity. The change in the viscosity component caused by this DMA is a very important physical property for predicting the properties of a solder photoresist whose Tg is lower than the melting temperature of the solder.

In particular, the variation of Tanδ obtained by DMA is of great significance. For materials with a large maximum value of the peak of Tanδ (such as materials with the physical properties shown in Figure 1), in order to alleviate the mechanical stress caused by mounting electronic parts For the purpose of sexual pressure, it is suitable for soft and soft components. On the other hand, materials with a smaller maximum value of the wave peak of Tan δ (such as materials with the physical properties shown in Figure 2) are more rigid and warm in order to resist pressure. less dependencies.

In addition, IC packaging in the future must also consider the latter method, that is, as long as the value of Tanδ of DMA is less than 0.15, the viscous component in the cured product will be less, so the viscous component will be reduced by thermal history. Part of the cross-linking reaction proceeds, and the cross-linking structure becomes loose due to molecular motion near Tg, which can suppress changes in physical properties. That is, since there is less temperature dependence and less change in physical properties before and after Tg, stress caused by changes in physical properties due to high temperature thermal history can be reduced. Therefore, as long as the value of Tanδ of DMA is 0.15 or less, not only the stress of (1) but also the stress suppression of (3) is effective.

In addition, in order to reduce the Tanδ of the cured product, the average particle size of the inorganic filler is set in a specific range, and a specific reactive group is further introduced into the inorganic filler, and the epoxy equivalent of the epoxy resin is set by setting the epoxy equivalent. In the range below the specific value, the stress of (2) is effective from the viewpoint of crosslinking and densification.

That is, the curable resin composition of the present invention contains (A) an alkali-soluble resin, (B) a thermosetting component, (C) a compound having an ethylenically unsaturated group, (D) a photopolymerization initiator, and (E) A resin composition of a surface-treated inorganic filler, characterized in that the (E) surface-treated inorganic filler has an average particle size of 100 nm to 1 μm, and has the properties of (A) the alkali-soluble resin, The aforementioned (B) thermosetting component and the aforementioned (C) tool At least one reactive group of the compound having an ethylenically unsaturated group reacted with, as the above-mentioned (B) thermosetting component, an epoxy resin having an epoxy equivalent weight of 300 g/eq. or less is included, and the thickness obtained from the above-mentioned resin composition is 40 μm When measuring the dynamic viscoelasticity from 25°C to 300°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C/min, the maximum value of Tanδ is 0.15 or less.

The curable resin composition of the present invention contains (B-1) a bifunctional or higher epoxy resin having a softening point of 40°C or lower and (B-2) a bifunctional or higher epoxy resin having a softening point of 40°C or higher as the aforementioned ring. The epoxy resin with an oxygen equivalent of 300 g/eq. or less is preferable.

In the curable resin composition of the present invention, the compounding amount of the (C) compound having an ethylenically unsaturated group is preferably less than 20 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin.

In the curable resin composition of the present invention, the blending amount of the (E) surface-treated inorganic filler is preferably 35% by mass or more in the solid content of the curable resin composition.

In the curable resin composition of the present invention, when the dynamic viscoelasticity of the cured product is measured from 25°C to 300°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C/min, the storage elastic modulus at 150°C is 1 GPa or more, In addition, the change rate of the storage elastic modulus from 25°C to 150°C is preferably within 70%.

In the curable resin composition of the present invention, the CTEα2 of the cured product is preferably 110 ppm or less.

In the curable resin composition of the present invention, the cured product The Tg is preferably above 160°C.

The curable resin composition of the present invention is preferably used for forming a solder photoresist.

The dry film of the present invention has a resin layer obtained by coating the aforementioned curable resin composition on a film and drying it.

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

The printed wiring board of this invention has the said hardened|cured material.

The present invention can provide a curable resin composition capable of obtaining a cured product excellent in crack resistance under a high temperature load, a dry film having a resin layer obtained from the composition, and the composition Or a cured product of the resin layer of the dry film, and a printed wiring board having the cured product.

[ Fig. 1] Fig. 1 is a graph showing the storage elastic modulus, loss elastic modulus, and Tan δ of a cured product having a large maximum value of the peak of Tan δ.

[ Fig. 2] Fig. 2 shows images of storage elastic modulus, loss elastic modulus, and Tan δ of a cured product having a small maximum value of the peak of Tan δ.

In the curable resin composition of the present invention, the maximum value of Tanδ of the cured product is 0.15 or less in the temperature range of 25 to 300°C. As long as it is such a physical property, even if the temperature of the cured film is exposed to a low temperature to a high temperature, it is possible to obtain Stable crack resistance.

In addition, in this specification, as long as the physical properties of the cured product such as Tanδ are not particularly limited, the resin layer after drying of the resin composition is irradiated with ultraviolet rays at a rate of about 500 mJ/cm ² , and further irradiated with ultraviolet rays in a UV conveyor belt furnace equipped with a high-pressure mercury lamp. Physical properties of a cured product with a thickness of 40 μm obtained by irradiating with an exposure amount of 1 J/cm ² and then heating at 160° C. for 60 minutes to completely cure the resin layer. In addition, ultraviolet rays are electromagnetic waves having a wavelength of 10 to 400 nm. Tanδ is the value obtained by dividing the loss elastic modulus measured by the dynamic viscoelasticity measurement by the storage elastic modulus, that is, the loss tangent (=loss elastic modulus/storage elastic modulus). In this specification, the dynamic viscoelasticity measurement is used to measure The physical properties such as Tanδ are based on graphs 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.

In order to obtain a cured product with a small Tanδ (= loss elastic modulus/storage elastic modulus), it is sufficient to reduce the loss elastic modulus (viscous component) or increase the storage elastic modulus (elastic component), and either In other words, it is better to increase the elastic component as much as possible than to increase the viscous component in the hardened product.

The means for setting the maximum value of Tan δ to 0.15 or less is not particularly limited, but an average particle diameter of 100 nm to 1 μm is used, and it has the properties of (A) alkali-soluble resin, (B) thermosetting component, and (C) Surface-treated non-reactive group of at least one reactive group in the compound of ethylenically unsaturated group It is effective to use an epoxy resin having an epoxy equivalent weight of 300 g/eq. or less as an organic filler and as the (B) thermosetting component.

(E) If the average particle diameter of the inorganic filler is 1 μm or less, the surface area per volume is large, and the above-mentioned reactive groups can be more abundant. On the other hand, when the average particle diameter is 100 nm or more, shrinkage of the cured product is suppressed, and crack resistance is improved.

In addition, by including an epoxy resin having an epoxy equivalent of 300 g/eq. or less as the (B) thermosetting component, since the number of crosslinking points with the (A) alkali-soluble resin increases, the crosslinking density increases, and the Reduce unreacted (A) alkali-soluble resin and the like. Therefore, the maximum value of Tan δ becomes small, the elastic modulus of the cured product does not change rapidly at a high temperature around 150°C, and the crack resistance is further improved.

Therefore, by curing the above-mentioned composition containing the inorganic filler (E) and an epoxy resin having an epoxy equivalent of 300 g/eq. or less, the maximum value of Tan δ of the cured product is in the range of 25 to 300° C. It will be 0.15 or less, and a stable crack resistance can be obtained. If the maximum value of Tanδ is 0.13 or less, it is preferable because of the crack resistance.

Furthermore, even if the compounding quantity of (C) the compound which has an ethylenically unsaturated group is made small as mentioned later, the Tan delta of hardened|cured material can be made small.

When the maximum value of Tanδ of the cured product is large, if the cured product is exposed to high temperature, the viscous component of the cured product will easily change, and the physical properties will change greatly. Even at a high temperature close to the Tg of the hardened product, the viscous component It hardly fluctuates, and the change in physical properties is small, and the occurrence of cracks can be suppressed.

The storage elastic modulus of the cured product of the curable resin composition of the present invention at 150°C may be any value as long as the maximum value of Tanδ of the cured product is 0.15 or less, but preferably 1 GPa or more. More preferably, it is 2GPa or more. If the storage elastic modulus is 1 GPa or more, the resistance of the cured product to the water vapor pressure inside the package will be improved, and the crack resistance or insulation reliability will be improved.

Furthermore, in order to obtain crack resistance at high temperature, it is preferable that the change in storage elastic modulus be large for stress absorption.

However, in the curable resin composition of the present invention, the change rate of the storage elastic modulus is reduced, so that the toughness can be maintained even at high temperature, and the generation of stress and the generation of cracks are suppressed.

In the present invention, the change rate of the storage elastic modulus is preferably small, and the change rate of the storage elastic modulus at 25°C to 150°C is preferably within 70%. More preferably, it is within 65%.

The CTEα2 of the cured product of the curable resin composition of the present invention is preferably 110 ppm or less, and more preferably 100 ppm or less. The smaller the CTEα2, the smaller the change in physical properties even at high temperatures.

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

Each component of the curable resin composition of this invention is demonstrated below. In addition, in this specification, (meth)acrylate refers to the general term of acrylate, methyl acrylate, and mixtures of these, and other similar terms The performance is the same.

[(A) Alkali-soluble resin]

(A) Alkali-soluble resins include, for example, resins containing one or more alkali-soluble groups among phenolic hydroxyl groups, thiol groups, and carboxyl groups, preferably compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, and phenolic Compounds with hydroxy and carboxyl groups, and compounds with two or more thiol groups. As the (A) alkali-soluble resin, a carboxyl group-containing resin or a phenolic hydroxyl group-containing resin can be used, but from the viewpoint of reactivity with the (B) thermosetting component and (E) inorganic filler, the carboxyl group-containing resin better.

Furthermore, (A) the weight average molecular weight of the alkali-soluble resin is small, the ratio of the alkali-soluble group of the alkali-soluble resin increases, and the crosslinking density of the cured product increases, which is preferable. (A) The weight average molecular weight of the alkali-soluble resin is preferably 10,000 or less in terms of polystyrene when measured by weight average molecular weight (Mw) colloid permeation chromatography (GPC).

(A) Alkali-soluble resin preferably has an ethylenically unsaturated group in the molecule in addition to the carboxyl group from the viewpoint of developability, photocurability, and development resistance. In addition, only the carboxyl group-containing resin which does not have an ethylenically unsaturated group may be used. As the ethylenically unsaturated group, acrylic acid, methacrylic acid, or derivatives thereof are preferred.

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

(1) A bifunctional or more polyfunctional epoxy resin is reacted with (meth)acrylic acid to add phthalic anhydride and tetrahydrol to the hydroxyl group present in the side chain. Carboxyl group-containing photosensitive resin of dibasic acid anhydrides such as phthalic anhydride and hexahydrophthalic anhydride. Here, it is preferable that the polyfunctional epoxy resin of bifunctional or more is solid.

(2) A polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid, and the carboxyl group-containing photosensitivity of a dibasic acid anhydride is added to the generated hydroxyl group. resin. Here, the bifunctional epoxy resin is preferably 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 compound such as (meth)acrylic acid monocarboxylic acid reaction, and then react the alcoholic hydroxyl group of the resulting reaction product with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride and other polybasic acid anhydrides. Carboxyl group photosensitive resin.

(4) Making bisphenol A, bisphenol F, bisphenol S, novolac-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxynaphthalene and aldehydes, 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 and propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid to make 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 and propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid to make Carboxyl-containing photosensitive tree obtained by reacting the obtained reaction product with a polybasic acid anhydride fat.

(6) By copolymerization of unsaturated carboxylic acid such as (meth)acrylic acid, and unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, and isobutylene The obtained carboxyl group-containing photosensitive resin.

(7) The polyfunctional tetracyclic ether resin described later is reacted with dicarboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, etc., and the resulting primary hydroxyl group is added to a carboxyl group-containing dibasic acid anhydride. polyester 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 a carboxyl group-containing resin such as the above (1) to (7) is added.

As a carboxyl group-containing resin having an ethylenically unsaturated group (also referred to as a carboxyl group-containing photosensitive resin), a structure in which the ethylenically unsaturated group in the main chain and the side chain derived from a phenol resin or an epoxy resin is separated is preferable . 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 formed between the main chain and the ethylenically unsaturated group. With such a structure, the reactivity of the ethylenically unsaturated groups in the side chains increases, which is preferable. As the carboxyl group-containing resin having a chain extension structure and an ethylenically unsaturated group, for example, the carboxyl group-containing resins described in the above (3), (4), (5), and (8) are preferred.

(A) The acid value of the alkali-soluble resin is preferably 40 to 150 mgKOH/g. By setting the acid value of the carboxyl group-containing resin to be 40 mgKOH/g or more, alkali development becomes more favorable. In addition, by setting the acid value to be 150 mgKOH/g or less, a normal cured product pattern can be easily drawn. More preferably, it is 50-130 mgKOH/g.

(A) The blending amount of the alkali-soluble resin is based on the total solid content of the composition from which the solvent is removed, and is, for example, 15 to 60 mass %, preferably 20 to 60 mass %. By being 15 mass % or more, preferably 20 mass % or more, the coating film strength can be improved. And by setting it as 60 mass % or less, the viscosity will be suitable and workability will be improved. More preferably, it is 30-50 mass %.

[(B) Thermosetting component]

The curable resin composition of the present invention contains an epoxy resin having an epoxy equivalent of 300 g/eq. or less as the (B) thermosetting component, in order to increase the crosslinking density and further improve the crack resistance, More preferably, it is 200 g/eq. or less.

The epoxy resin is not particularly limited as long as it satisfies the above-mentioned epoxy equivalent. Examples of epoxy resins include epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; sulfide type epoxy resin; brominated epoxy resin; Epoxy resin; Biphenol novolac type epoxy resin; Bisphenol F type epoxy resin; Hydrogenated bisphenol A type epoxy resin; Glycidylamine type epoxy resin; Hydantoin type epoxy resin; Alicyclic Formula epoxy resin; trihydroxytoluene type epoxy resin; alkanol type epoxy resin (such as double phenol type epoxy resin); biphenol type epoxy resin; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetraphenylmethane type epoxy resin; heterocyclic epoxy resin; diglycidyl phthalic acid resin; tetraglycidyl phenol ethane resin; naphthyl-containing epoxy resin; Epoxy resin with diene skeleton; triphenylmethane type epoxy resin; epoxy resin with silsesquioxane skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexylmaleimide Copolymerized epoxy resin of glycerol methacrylate; epoxy modified polybutadiene rubber derivative; CTBN modified epoxy resin, etc. An epoxy resin can be used individually by 1 type or in combination of 2 or more types. Among them, especially novolac type epoxy resin, bisphenol type epoxy resin, bisphenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, naphthalene type epoxy resin , at least any one of an epoxy resin having a silsesquioxane skeleton and a triphenylmethane epoxy resin is preferred.

Commercially available epoxy resins having an epoxy equivalent weight of 300 g/eq. or less include EXP7241 (triphenylmethane type epoxy resin), HP6000 (epoxy resin having a naphthyl group), and Epiclon N manufactured by DIC Corporation. -740 (phenol novolac epoxy resin), Epototo YDC-1312 (hydroquinone epoxy resin), YSLV-80XY (bisphenol F epoxy resin), etc. manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.

Since the composition of the present invention can further increase the crosslinking density, it is preferable to include two or more types of polyfunctional epoxy resins as the (B) thermosetting component from the viewpoint of lowering Tanδ. In this specification, "polyfunctional" means two or more functionalities. Furthermore, the composition of the present invention preferably contains (B-1) a bifunctional or higher epoxy resin having a softening point of 40° C. or less as the (B) thermosetting component, and contains the (B-1) component and (B-1) -2) A mixture of epoxy resins having a softening point of more than 40° C. having a bifunctional or more functions is preferable. By including (B-1) a bifunctional or higher epoxy resin having a softening point of 40°C or lower, (E) inorganic filler The filling agent can be highly filled, and has low CTE and low Tanδ, and the crack resistance will be improved in the temperature cycle test. Furthermore, the glass transition temperature (Tg) of the whole curable resin composition can be raised by also containing (B-2) the bifunctional or more epoxy resin whose softening point exceeds 40 degreeC. As a result, reliability such as heat resistance such as PCT resistance and crack resistance in a temperature cycle test can be further improved. Here, the softening point means a value measured by the method described in JIS K 7234.

(B-1) As the bifunctional or higher epoxy resin having a softening point of 40° C. or lower, known resins are exemplified, and for example, it is preferable to be in a liquid state at room temperature. (B-1) As commercially available epoxy resins having a softening point of 40° C. or lower with bifunctional or higher functions, for example, Epikote 834, 828 (manufactured by Mitsubishi Chemical Corporation), and YD-128 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) , 840, 850 (manufactured by DIC Corporation) and other bisphenol A epoxy resins, 806, 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation), 830, 835, N-730A ( DIC Corporation) and other bisphenol F epoxy resins, ZX-1059 (Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) and other mixtures of bisphenol A and bisphenol F, YX-8000, 8034 (Mitsubishi Chemical Corporation) ST -3000 (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.) hydrogenated bisphenol A type epoxy resin, RE-306CA90 manufactured by Nippon Kayaku Co., Ltd., DEN431, DEN438 manufactured by Dow Chemical Co., Ltd. Novolak type epoxy resin, Alkanol type epoxy resins such as Epiclon HP-820 manufactured by DIC Corporation.

(B-1) The content of the epoxy resin having a softening point of 40°C or lower is 40°C or higher with respect to 1 equivalent of the alkali-soluble group of the (A) alkali-soluble resin, and (B-1) The softening point of the bifunctional epoxy resin having a softening point of 40°C or lower above epoxy resin The epoxy group is preferably in the range of 0.2 to 1.8 equivalents. (B-1) The softening point of the epoxy resin having a softening point of 40°C or less and having a bifunctional or higher function is preferably -80 to 30°C, more preferably -70 to 20°C. (E) In order to increase the filling of inorganic fillers, which are effective in reducing Tan δ, using epoxy resins having a softening point of 40°C or lower with bifunctional or higher functions can increase the degree of freedom of compounding design and increase the Then strength.

(B-2) Commercially available epoxy resins having a softening point of more than 40° C. bifunctional or higher include ICTEP-S (softening point: 110° C.), TEPIC-H, N870, DIC manufactured by Nissan Chemical Co., Ltd. Company-made HP-7200 (softening point: 60°C), HP-4700 (softening point: 90°C), HP-4710 (softening point: 96°C), EXA-7241 (softening point: 70°C), Mitsubishi Chemical Corporation YX-4000 (softening point: 105°C) manufactured by Nippon Kayaku Co., Ltd., NC-3000L (softening point: 52°C), NC-7000L (softening point: 86°C), CER-3000L (softening point: 93°C) ), EPPN-502H (softening point: 67°C), Epototo YSLV-80XY (softening point: 80°C) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., EPICLON-N660 (softening point: 61~69°C), Nippon Steel Sumitomo Metal Epototo YDC-1312 (softening point: 140° C.) manufactured by Chemical Co., Ltd., and the like.

(B-2) The softening point of the bifunctional or higher epoxy resin having a softening point of more than 40°C is preferably 50°C or higher, more preferably 60°C or higher. Furthermore, (B-2) The upper limit of the softening point of the epoxy resin having a softening point exceeding 40°C of bifunctional or higher is not particularly limited, but is about 400°C or lower. From the viewpoint of workability during dry film formation, it is preferably 80° C. or lower.

(B-1) Epoxy having a softening point of 40° C. or lower with bifunctional or higher functions The mixing ratio of resin and (B-2) epoxy resin whose softening point exceeds 40°C is (B-1) epoxy group (b-1) and epoxy group (b-1) of epoxy resin whose softening point is 40°C or lower and which is more than bifunctional. (B-2) The equivalence ratio (b-1) of epoxy groups (b-2) of epoxy resins having a softening point of more than 40° C. with bifunctional or higher: (b-2) is 3:7~9:1. Better, more preferably 4:6~8:2. By setting the ratio of the epoxy group (b-1) to 3 to 9, it is possible to achieve both low Tanδ and high Tg.

As an epoxy resin whose epoxy equivalent is 300 g/eq. or less, among epoxy resins, the epoxy resin containing trifunctional or more is particularly preferable from the viewpoint of improving the crosslinking density. The structure of the trifunctional or more epoxy resin is not particularly limited, as long as it is an epoxy resin having three or more epoxy groups. Among these, from the viewpoint of further improving the crosslinking density, an epoxy resin having an epoxy equivalent of 200 g/eq. or less with trifunctional or more is more preferable.

As a specific example of a commercially available epoxy resin having a trifunctional or more than trifunctional epoxy group, a trifunctional aminophenol type epoxy resin has a trade name "jER-630" (manufactured by Mitsubishi Chemical Co., Ltd.), a trifunctional epoxy resin The trade name of epoxy resin with triazabenzene skeleton is "TEPIC-SP" (manufactured by Nissan Chemical Industry Co., Ltd.), the trade name of trifunctional aromatic epoxy resin is "Techmore VG3101" (manufactured by Printech Corporation), and the tetrafunctional aromatic ring The trade name of oxygen resin "GTR-1800" (manufactured by Nippon Kayaku Co., Ltd.), the trade name of denatured novolak type epoxy resin "EPICLON-N740" (manufactured by DIC Corporation), and the trade name of dicyclopentadiene type epoxy resin "EPICLON-HP7200H-75M" (manufactured by DIC Corporation), trade name of cresol novolak type epoxy resin "EPICLON-N660" (manufactured by DIC Corporation), trade name of novolak type epoxy resin "jER-152" ” (manufactured by Mitsubishi Chemical Corporation), one of epoxy resins containing a biphenyl skeleton Trade name "NC3000" (manufactured by Nippon Kayaku Co., Ltd.), "NC3000H" (manufactured by Nippon Kayaku Co., Ltd.), "NC3000L" (manufactured by Nippon Kayakuyo Co., Ltd.), and trade name of naphthalene-type epoxy resin "ESN-175S" (new manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), etc.

(B) As a thermosetting component, among the said epoxy resins, the epoxy resin which has a silsesquioxane skeleton can be used more suitably. By blending an epoxy resin having a silsesquioxane skeleton, the proportion of inorganic components in the composition increases and the viscous component decreases. Thereby, the maximum value of Tan δ becomes small, and the hardened material becomes difficult to harden and shrink at high temperature. As the epoxy resin having a silsesquioxane skeleton, silsesquioxane, that is, a network polymer having a structure of (RSiO _1.5 ) _n obtained by hydrolyzing a trifunctional silane is exemplified. The compound or the polyhedral polymer, and the compound having an epoxy group-containing group is not particularly limited. Each silicon of silsesquioxane is bonded to an average of 1.5 oxygen atoms and 1 hydrocarbyl group.

The epoxy resin having a silsesquioxane skeleton preferably has a silsesquioxane skeleton represented by the following general formula (1).

(in the formula, R ¹ to R ⁴ are each independently a group having a SiO bond or an organic group, and at least one of R ¹ to R ⁴ is a group having an epoxy group), here, the organic group means that it contains carbon atoms foundation.

The structure of the aforementioned silsesquioxane is not particularly limited, and silsesquioxane having a well-known and conventional structure such as a random structure, a trapezoidal structure, a complete cage structure, and an incomplete cage structure can be used.

The groups having SiO bonds that can be obtained from R ¹ to R ⁴ are not particularly limited, and examples include groups having SiO bonds and aliphatic skeletons, groups having SiO bonds and aromatic skeletons, and groups having SiO bonds. It is preferable that the group of a junction and a heteroatom be within the range of the equivalent of the above-mentioned thermosetting functional group (epoxy group).

Although it does not specifically limit as an organic group containing carbon atoms which can be obtained by R ¹ to R ⁴ , and examples thereof include aliphatic groups such as methyl groups, aromatic groups such as phenyl groups, and groups having hetero atoms. It is preferably an organic group having 1 to 30 carbon atoms, and it is preferably within the range of the equivalent of the above-mentioned thermosetting functional group (epoxy group).

At least one of R ¹ to R ⁴ is a group having an epoxy group, and here, 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.

The blending amount of the (B) thermosetting component is, for example, 1 to 100 parts by mass, preferably 10 to 80 parts by mass, more preferably 20 to 60 parts by mass, relative to 100 parts by mass of the (A) alkali-soluble resin. (B) When the blending amount of the thermosetting component is 1 part by mass or more, crack resistance and insulation reliability are improved, and when it is 100 parts by mass or less, storage stability is improved.

The curable resin composition of the present invention may contain epoxy having an epoxy equivalent of 300 g/eq. or less within a range that does not impair the effects of the present invention. Well-known thermosetting components other than resins. Amine resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, etc., isocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, and epoxy resins with an epoxy equivalent of more than 300 g/eq. can be used , known compounds such as tetracyclic ether compounds, episulfide resins, bismaleimide resins, carbodiimide resins, etc. 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 plural cyclic (thio) ether groups in the molecule is a compound having plural cyclic (thio) ether groups in the molecule of 3-, 4- or 5-membered rings, such as compounds having plural epoxy groups in the molecule, That is, a polyfunctional epoxy compound, a compound having plural propylene oxide groups in the molecule, that is, a polyfunctional tetracyclic ether compound, a compound having plural thioether groups in the molecule, that is, a polyfunctional episulfide resin, etc.

[(C) Compounds having ethylenically unsaturated groups]

The curable resin composition of the present invention contains (C) a compound having an ethylenically unsaturated group. As (C) a compound having an ethylenically unsaturated group, it is preferable to use a compound having one or more ethylenically unsaturated groups in the molecule. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like of a known and conventional compound having an ethylenically unsaturated group can be used. In addition, (C) the compound which has an ethylenically unsaturated group mentioned here does not contain the (A) alkali-soluble resin which has an ethylenically unsaturated group, and (E) the surface-treated inorganic filler.

Examples of photopolymerizable oligomers include unsaturated polyester-based Oligomers, (meth)acrylate-based oligomers, and the like. Examples of (meth)acrylate-based oligomers include novolak epoxy (meth)acrylate, cresol novolak epoxy (meth)acrylate, and bisphenol epoxy (meth)acrylate. Epoxy (meth)acrylate, urethane (meth)acrylate, epoxyurethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc. ) acrylate, polybutadiene modified (meth)acrylate, etc.

Examples of the photopolymerizable vinyl monomer include well-known and conventional ones, such as styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl acetate, vinyl butyrate, vinyl benzoate, and the like The vinyl esters; ethylene isobutyl ether, ethylene-n-butyl ether, ethylene-t-butyl ether, ethylene-n-dipentyl ether, ethylene isodiamyl ether, ethylene-n-octadecyl ether, ethylene Vinyl ethers such as cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether, etc.; acrylamide, methacrylate, N-methylol acrylamide, N -(Meth)acrylamides such as methylol methacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, etc. Amines; allyl compounds of triallyl isocyanate, diallyl phthalate, diallyl isophthalate, etc.; 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfural (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, etc. ( Esters of meth)acrylic acid; hydroxyalkyl (meth)acrylates of hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri (meth)acrylate, etc.; methyl Oxyethyl (meth)acrylate, ethoxyethyl (meth) Alkoxyalkylene glycol mono(meth)acrylates such as acrylates; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl ethylene glycol Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate Alkylidene polyol poly(meth)acrylate such as meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, ethoxylated trihydroxyl Polyoxyalkylene glycol poly(meth)acrylates such as methylpropanetriacrylate, propoxytrimethylolpropanetri(meth)acrylate, etc.; Neopentylglycol hydroxypivalate Poly(meth)acrylates such as (meth)acrylates; isocyanate-type poly(meth)acrylates such as [(meth)acryloyloxyethyl]isocyanate and the like. These characteristics required for coordination can be used alone or in combination of two or more.

(C) The compounding amount of the compound having an ethylenically unsaturated group is preferably less than 20 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin, more preferably 5 to 18 parts by mass, and still more preferably 10 to 15 parts by mass. By reducing the compounding amount of the compound having an ethylenically unsaturated group (C), the unreacted compound having an ethylenically unsaturated group in the cured product can be reduced, and the loss modulus (viscosity component) can be reduced.

[(D) Photopolymerization Initiator]

As the (D) photopolymerization initiator, any one can be used as long as it is a photopolymerization initiator known as a photopolymerization initiator or a photoradical generator.

Examples of the photopolymerization initiator include bis-(2,6-dichlorobenzyl)phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-2,5-dimethyl Phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthylphosphine oxide -(2,6-Dimethoxybenzyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, bis- (2,6-Dimethoxybenzyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzyl)-phenylphosphine oxide (BASF JAPAN IRGACURE819) and other bisphosphonium phosphine oxides; Methyl benzylphenyl phenylphosphonate, 2-benzoic acid methyl phenyl phosphine dioxide, trimethyl ethyl phenyl phenyl phosphonate isopropyl, 2,4,6-trimethylbenzyl Monoacyl phosphine oxides such as acyl phosphine dioxide (IRGACURETPO, manufactured by BASF JAPAN); 1-hydroxy-cyclohexyl phenone, 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}- Oxyacetophenones such as 2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.; Benzoin, Benzyl, Benzoin Methyl Ether, Benzoin Ether, Benzoin n - Benzoins such as propyl ether, benzoin isopropyl ether, benzoin n-butyl ether, etc.; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methyl bis Benzophenones such as benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamine benzophenone, etc.; acetophenone, 2,2-dimethoxy- 2-Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenone, 2-methyl-1- [4-(Methylthio)phenyl]-2-morpholinyl-1-propanone, 2-benzyl-2-dimethylamine-1-(4-morpholinylphenyl)-butanone-1 , 2-(Dimethyl Amine)-2-[(4-methylphenyl)methyl)-1-[4-(4-morphoyl)phenyl]-1-butanone, N,N-dimethylamine acetophenone and other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. thioxanthone Butyl scallion, 1-chloro scallion, 2-amino scallion, 2-amino scallion, etc. scallion; ketal such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Benzoic acid esters such as ethyl-4-aminobenzoic acid dimethyl ester, 2-(dimethylamine) benzoic acid ethyl ester, p-dimethyl benzoic acid ethyl ester, etc.; 1,2-octane Diketone, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)], ethanone, 1-[9-ethyl-6-(2-benzoic acid methyl)- Oxime esters such as 9H-carbazolyl-3-yl]-, 1-(O-acetyl oxime); 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-1 -yl) ethyl) phenyl] titanium etc. titanium sine; Sulfurized phenyl 2-nitrosoin, butyroin, anisin ethyl ether, azobisisobutyronitrile, disulfide tetramethylamine thiocarboxylate Wait. A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, monoacylphosphine oxides and oxime esters are preferred, and oxime esters with high sensitivity are preferred. As the oxime esters, those having one or more oxime ester groups are preferred, for example, ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl)-9H-carbazolyl-3 -Base]-, 1-(O-acetyl oxime) is more preferable.

The blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. When it is 0.5 parts by mass or more, the surface hardening property becomes relatively good, and when it is 20 parts by mass or less, halation hardly occurs, and good resolution can be obtained.

[(E) Surface-treated inorganic filler]

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

The inorganic filler is not particularly limited, and commonly used fillers are known. For example, silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, mica, clay, magnesium carbonate, carbonic acid can be used. Inorganic fillers such as calcium, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, asbestos, aluminum silicate, calcium silicate, and zinc. Among them, silicon dioxide is preferred, since the surface area will be reduced, and the stress will be dispersed in the whole, so it is difficult to become the starting point of cracks, and because of its excellent resolution, spherical silicon dioxide is more preferred.

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

As a cyclic (thio)ether group, an epoxy group, a propylene oxide group, an episulfide group etc. are mentioned, for example.

As an acidic group, a carboxyl group, a phenolic hydroxyl group, an alcoholic hydroxyl group, a thiol group, a thiol group, a phosphoric acid group, etc. are mentioned, for example.

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 (meth)propylene Any one of an acyl group, a vinyl group, and a cyclic (thio)ether group is preferable. (E) If the reactive group of the surface-treated inorganic filler is a cyclic (thio)ether group, the reactivity with the (A) alkali-soluble resin is excellent, and if it is a (meth)acryloyl group or a vinyl group , the reactivity with (A) the ethylenically unsaturated group of the alkali-soluble resin is excellent.

The method of introducing the aforementioned reactive group into the inorganic filler is not particularly limited, as long as it is introduced by a known and conventional method, as long as it is a surface treatment agent having the aforementioned reactive group, such as a coupling agent having the aforementioned reactive group Wait until the surface of the inorganic filler is processed.

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

As a silane coupling agent capable of introducing the above-mentioned reactive group into an inorganic filler, a silane coupling agent having a vinyl group, a silane coupling agent having a methacrylic group, a silane coupling agent having an acrylic group, and a silane coupling agent having an epoxy group are exemplified. A silane coupling agent, a silane coupling agent having a carboxyl group, etc., among them, a silane coupling agent having at least one of a (meth)acrylic group and a vinyl group is preferable.

(E) The surface-treated inorganic filler only needs to be blended into the curable resin composition of the present invention in a surface-treated state, or the untreated surface-treated inorganic filler and the surface treatment agent can be blended separately, and added to the curable resin composition of the present invention. In the composition, the inorganic filler is surface-treated, but it is preferable to pre-mix the surface-treated inorganic filler. By pre-blending the inorganic filler after surface treatment, it can prevent that the residual surface treatment cannot be consumed when blending separately. The crack resistance caused by the surface treatment agent is reduced. In the case of pre-surface treatment, it is preferable to mix the pre-dispersion liquid of pre-dispersed inorganic filler in the solvent or resin component, pre-disperse the inorganic filler after surface treatment in the solvent, and then mix the pre-dispersion liquid into the composition , or when the surface-untreated inorganic filler is preliminarily dispersed in a solvent, it is more preferable to mix the preparative dispersion into the composition after sufficient surface treatment.

(E) The average particle size of the surface-treated inorganic filler is preferably 100-800 nm, even more preferably 100-700 nm, and even more preferably 200-700 nm. In addition, in this specification, (E) the average particle diameter of the surface-treated inorganic filler is not only the particle diameter of primary particles, but also the average particle diameter (D50) including the particle diameter of secondary particles (aggregates). The average particle diameter can be determined by a laser diffraction particle size distribution analyzer. As a measuring device of the laser diffraction method, there is a Nanotrac wave manufactured by Nikkiso Co., Ltd., and the like.

(E) The higher the blending amount of the surface-treated inorganic filler, the higher the storage elastic modulus, the smaller the Tanδ, and the more difficult it is for the hardened material to expand, so (E) the blending amount of the surface-treated inorganic filler The total amount of the solid content of the curable resin composition is preferably 35% by mass or more. More preferably, it is 38-80 mass %.

(Thermosetting catalyst)

The curable resin composition of the present invention preferably contains a thermosetting catalyst. Examples of such a thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole Imidazole derivatives such as azoles; dicyandiamine, benzyldimethylamine, 4-(dimethylamine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-diamine Amine compounds such as methylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc., hydrazine compounds such as adipic acid dihydrazide, sebacate dihydrazine, etc.; triphenylphosphine, etc. Phosphorus compounds, etc. In addition, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamine-6-methacrylateoxyethyl-S-triazabenzene, 2-ethylene-2,4 can also be used -Diamine-S-triazabenzene, 2-ethylene-4,6-diamine-S-triazabenzene. Isocyanuric acid adduct, 2,4-diamine-6-methacrylic acid oxyethyl-S-triazabenzene. S-trazine derivatives such as isocyanuric acid adducts are preferably used in combination with a thermosetting catalyst and a compound which can also function as an adhesion imparting agent.

The blending amount of the thermosetting catalyst is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the (B) thermosetting component.

(hardener)

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

(Colorant)

The curable resin composition of the present invention may contain a colorant. As the colorant, known coloring agents such as red, blue, green, yellow, black, and white can be used. The agent can also be any one of pigments, dyes, and pigments. However, from the viewpoint of reducing the environmental load and the influence on the human body, it is preferable to not contain halogen.

The addition amount of the colorant is not particularly limited, but is preferably 10 parts by mass or less, particularly preferably 0.1 to 7 parts by mass, relative to 100 parts by mass of the (A) alkali-soluble resin.

(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 at the time of coating on a substrate or a carrier film. As the organic solvent, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Ethyl 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, Selusyl Acetate, Butyl Selussell Acetate, Carbitol Acetate, Butyl Carbitol Acetate, Propylene Glycol Esters of monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum-based solvents such as petroleum ether, naphtha, and solvent naphtha and other well-known and commonly used organic solvents. These organic solvents can be used alone or in combination of two or more.

(any other ingredients)

Further, the curable resin composition of the present invention may be blended with other additives that are well-known and commonly used in the field of electronic materials. as other additions Agents include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, anti-charge agents, anti-aging agents, antibacterial and antifungal agents, antifoaming agents, leveling agents, and tackifiers , Adhesion imparting agent, thixotropy imparting agent, light start aid, sensitizer, thermoplastic resin, organic filler, release agent, surface treatment agent, dispersant, dispersing aid, surface modifier, stabilizer , phosphors, AB-type or ABA-type block copolymers, etc.

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

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 forming a dry film, first, after diluting the curable resin composition of the present invention with the above-mentioned organic solvent and adjusting it to an appropriate viscosity, it is applied by a notch coater, a blade coater, a rip coater, a bar coater, Extrusion coater, reverse coater, transfer roller coater, gravure coater, spray coater, etc., coat the carrier film to a uniform thickness. After that, a resin layer can be formed by drying the coated composition at a temperature of usually 40 to 130° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but the film thickness after drying is generally 3 to 150 μm, preferably 5 to 60 μm, and is appropriately selected.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyimide film, a polypropylene film, and a polystyrene film can be used. film etc. There is no special limit on the thickness of the carrier film, generally 10~ It is appropriately selected within the range of 150 μm. More preferably, it is the range of 15-130 micrometers.

For the purpose of preventing dust from adhering to the surface of the resin layer after forming the resin layer of the curable resin composition of the present invention on the carrier film, a cover film that can be peeled off on the surface of the resin layer is preferred. As the peelable cover film, for example, a polyethylene film or a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. As the cover film, when the cover film is peeled off, it may be smaller than the adhesive force between the resin layer and the carrier film.

Moreover, in this invention, the curable resin composition of this invention is apply|coated to the said coverlay film, and it is made to dry to form a resin layer, and a carrier film can also be laminated|stacked on the surface. That is, when producing a dry film in the present invention, either a carrier film or a cover film may be used as a film to which the curable resin composition of the present invention is applied.

The printed wiring board of this invention has the curable resin composition of this invention, or the hardened|cured material obtained by the resin layer of a dry film. As the manufacturing method of the printed wiring board of the present invention, for example, the curable resin composition of the present invention is adjusted to a viscosity suitable for the coating method by using the above-mentioned organic solvent, by dip coating method, flow coating method, roll coating method , rod coating method, screen printing method, curtain coating method, etc. are applied to the substrate, and the organic solvent contained in the composition is volatilized and dried at a temperature of 60~100 ° C (temporary drying), thereby forming Non-sticky resin layer. And, when it is dry film. The resin layer is formed on the base material by peeling off the carrier film after the resin layer is brought into contact with the base material by a laminating machine or the like and bonded to the base material.

As the above-mentioned substrates, in addition to printed wiring boards or flexible printed wiring boards formed with copper or the like in advance, there are also paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/ Non-woven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, using fluororesin. Polyethylene. Polyphenylene ether, polyoxyphenylene oxide. Materials such as cyanate ester and other high-frequency circuit copper laminates, and copper laminates of all grades (FR-4, etc.), and metal substrates, polyimide films, and PET films. , Polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer plate, etc.

The volatilization drying after applying the curable resin composition of the present invention can be performed using a hot air circulating drying furnace, an IR furnace, a hot plate, a convection oven, etc. The method of contact with the flow and the method of blowing the support with a nozzle) are carried out.

After the resin layer is formed on the printed wiring board, it is selectively exposed to active energy rays through a mask with a specific pattern formed, and the unexposed part is exposed to a diluted alkaline aqueous solution (for example, 0.3 to 3 mass % carbonated soda aqueous solution). Like, forming a pattern of hardened objects. Further, the hardened material is irradiated with active energy rays and then heated and hardened (for example, 100 to 220° C.), or heated and hardened and then irradiated with active energy rays, or only heated and hardened and then hardened at the final finishing stage (primary hardening), thereby forming a dense A cured film with excellent adhesion, hardness and other properties.

The exposure machine used for the above-mentioned active energy ray irradiation may be any device equipped with a high-pressure mercury-vapor bulb, an ultra-high-pressure mercury-vapor bulb, a metal halide bulb, a mercury short-arc bulb, or the like, which irradiates ultraviolet rays in the range of 350 to 450 nm. , and can also use a direct drawing device (eg, a laser direct imaging device that draws a portrait with a direct laser using CAD data from a computer). It can also be used as a light bulb light source or a laser light source for a direct-drawing machine, and the maximum wavelength is in the range of 350~450nm. The exposure amount for image formation varies depending on the film thickness, etc., but is generally 10 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .

As the above-mentioned developing method, a dipping method, a shower method, a spraying method, a brushing method, etc. can be used, and as the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkali solutions of ammonia, amines, etc.

The curable resin composition of the present invention is suitable for forming a cured film on a printed wiring board, further suitable for forming a permanent film, and more suitable for forming a solder photoresist, an interlayer insulating layer, and a cladding layer. Moreover, it is suitable for the formation of printed wiring boards with wiring patterns of fine pitch requiring high reliability, such as packaging substrates, especially the formation of permanent films (especially solder photoresists) for FC-BGA. In particular, the curable resin composition of the present invention can obtain a cured product excellent in crack resistance when a high temperature load is applied, and is therefore suitable for applications exposed to high temperatures such as 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, below, "part" and "%" are all quality standards unless there is a particular limitation.

[Synthesis of Alkali-Soluble Resin A-1]

Into an autoclave equipped with a thermometer, a nitrogen introduction device and an alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolak-type cresol resin (trade name "Shownor CRG951", manufactured by Showa Polymer Co., Ltd., OH equivalent: 119.4), 1.19 parts of potassium hydroxide and 119.4 parts of toluene were substituted with nitrogen in the system while stirring, and the temperature was heated. Next, 63.8 parts of propylene oxides were dripped gradually, and it was made to react at 125-132 degreeC at 0-4.8 kg/cm< ² > for 16 hours. After that, it was cooled to room temperature, 1.56 parts of 89% phosphoric acid was added to the reaction solution and mixed, and potassium hydroxide was neutralized to obtain a nonvolatile content of 62.1% and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.) Propylene oxide reaction solution of novolak cresol resin. This is an average of 1.08 moles of added propylene oxide per equivalent of phenolic hydroxyl group.

293.0 parts of the propylene oxide reaction solution of the obtained novolak-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone, and 252.9 parts of toluene were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing pipe In the medium, air was blown in at a rate of 10 m1/min, and the mixture was reacted at 110° C. for 12 hours while stirring. 12.6 parts of water was distilled off as an azeotrope with toluene from the water produced by the reaction. Then, it cooled to room temperature, the obtained reaction solution was neutralized with 35.35 parts of 15% sodium hydroxide aqueous solutions, and it wash|cleaned with water. Then, it distilled off, substituting toluene into 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator, and obtained the novolak-type acrylate resin solution. Next, 332.5 parts of the obtained novolak-type acrylate resin solution and triphenyl 1.22 parts of phosphine was introduced into a reactor equipped with a stirrer, a thermometer and an air blowing pipe, and air was blown in at a rate of 10 ml/min. It was made to react at C for 6 hours, and it was taken out after cooling. Thus, a solution of the carboxyl group-containing photosensitive resin A-1 with a nonvolatile content of 65% and a solid acid value of 87.7 mgKOH/g was obtained.

[Synthesis of Alkali-Soluble Resin A-2]

Into 700 g of diethylene glycol monoethyl ether acetate, 1070 g of n-cresol novolak type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, softening point 95°C, epoxy equivalent 214, average reactivity base 7.6) was placed (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 heated to 100° C. and stirred to dissolve uniformly.

Next, 4.3 g of triphenylphosphine was placed, heated to 110° C. and reacted for 2 hours, and then 1.6 g of triphenylphosphine was further added, and the temperature was raised to 120° C. and further reacted for 12 hours. In the obtained reaction liquid, 562 g of aromatic hydrocarbons (Solvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were put, and the reaction was carried out at 110° C. for 4 hours. Furthermore, 142.0 g (1.0 mol) of methyl glycidyl acrylate was put in the obtained reaction liquid, and it was made to react at 115 degreeC for 4 hours, and the photosensitive resin solution (A-2) containing a carboxyl group was obtained.

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

[Synthesis of epoxy resin with silsesquioxane skeleton B-1]

90.0 parts of γ-glycidoxypropyltrimethoxysilane, 3.0 parts of phenyltrimethoxysilane, 2.0 parts of methyltrimethoxysilane, 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 wt % potassium hydroxide aqueous solution was continuously dropped over a period of 30 minutes. After the dropping was completed, the resulting methanol was removed and allowed to react at 80° C. for 5 hours. After the reaction, washing with water was repeated until the washing liquid became neutral. Next, by removing the solvent under reduced pressure, 69 parts of epoxy resins having a silsesquioxane skeleton were obtained. 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 (Silicon Dioxide) E-1]

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

[Adjustment of Surface-treated Inorganic Filler (Silicon Dioxide) E-2]

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

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

The above-mentioned resin solution (varnish) is mixed with the various components shown in Tables 1 to 3 in the proportions (parts by mass) shown in Tables 1 to 3. After pre-mixing with a mixer, kneading is carried out with three rolling mills. A curable resin composition is prepared.

<Production of dry film>

To the curable resin composition obtained above, 300 g of methyl ethyl ketone was added, diluted, and stirred with a mixer for 15 minutes to obtain a coating liquid. Apply the coating solution on a polyethylene terephthalate film (Enlette PTH-25, manufactured by Unitika) with an arithmetic surface roughness of Ra150nm and a thickness of 38μm, and dry it at a temperature of 80°C for 15 minutes to form a photosensitive film with a thickness of 20μm. resin layer. Next, the 18-micrometer-thick polypropylene film (OPP-FOA by Futamura company) was bonded together on the photosensitive resin layer, and the photosensitive dry film was produced.

<Preparation of hardened coating>

On the low-profile copper foil, the polyethylene film was peeled off from the photosensitive dry film obtained as described above, and the photosensitive resin layer of the photosensitive dry film was pasted on the surface side of the copper foil. MVLP-500) was prepared, and the laminate was heated under the conditions of pressure degree: 0.8 MPa, 70° C., 1 minute, and vacuum degree: 133.3 Pa, so that the substrate and the photosensitive resin layer were adhered.

Next, after exposure (exposure amount: 400-600 mJ/cm ² ) from the photosensitive dry film using an exposure device mounted on a high pressure mercury lamp (short arc bulb), the polyethylene terephthalate film was peeled off from the photosensitive dry film to expose the photosensitive resin layer. Then, use 1 wt % Na ₂ CO ₃ aqueous solution at 30° C. and spray pressure of 2 kg/cm ² for 60 seconds of development to form a resin layer with a specific photoresist pattern. Next, after irradiating the resin layer with an exposure amount of 1 J/cm ² in a UV conveyor furnace equipped with a high-pressure mercury lamp, the resin layer was heated at 160° C. for 60 minutes to completely cure the resin layer, and a cured coating film was produced.

<Evaluation of Tanδ, Tg, and storage elastic modulus>

The cured coating film obtained as described above was peeled off from the copper foil, and the sample was cut out to measure the size (size of 5 mm × 10 mm). The temperature was increased from 25°C to 300°C by 5°C/min with DMS6100 manufactured by Hitachi Hightech, and the frequency was 1 Hz. Measured in stretched sine wave mode.

Tanδ is the maximum value in the temperature measurement area, and the temperature at this time is taken as Tg, and the storage elastic modulus (E') is obtained from data at 25°C (E'1) and 150°C (E'2).

The rate of change of the storage elastic modulus (E') was calculated by (E'1-E'2)/E'1 using the storage elastic modulus of the above-mentioned two points.

<Assessment of CTE>

The cured coating film obtained as described above was peeled off from the copper foil, a sample was cut out to obtain a measurement size (size of 3 mm×10 mm), and CTE was measured with TMA6100 manufactured by Hitachi Hightech. The measurement conditions were that the test load was 5 g, the sample was heated from room temperature at a temperature increase rate of 10°C/min, and the temperature was repeated twice to obtain the linear expansion coefficient (CTE(α2)) above the second Tg.

<Crack resistance (TCT resistance)>

The surface of the substrate (50mm x 50mm x 0.4mmt) connected to C4 with a loop forming a 250μm concave-convex pitch was chemically polished, and the polyethylene film was peeled off from the photosensitive dry film obtained as described above, and the surface on the polished side was attached. The photosensitive resin layer of the photosensitive dry film was then heated using a vacuum laminating machine (MVLP-500 manufactured by Meiki Seisakusho) under the conditions of pressure degree: 0.8MPa, 70°C, 1 minute, vacuum degree: 133.3Pa The laminate is used to adhere the substrate and the photosensitive resin layer. Next, using an exposure device equipped with a high-pressure mercury lamp (short-arc bulb), through an exposure mask with a negative pattern of 70 μm in diameter, the photosensitive dry film was exposed to light, and then the polyethylene terephthalate was peeled off from the photosensitive dry film. The formate film exposes the photosensitive resin layer. Then, use 1 wt % Na ₂ CO ₃ aqueous solution at 30° C. and spray pressure of 2 kg/cm ² for 60 seconds of development to form a resin layer with a specific photoresist pattern. Next, after irradiating the resin layer with a UV conveyor belt furnace equipped with a high-pressure mercury lamp and an exposure amount of 1 J/cm ² , the resin layer is completely cured by heating at 160° C. for 60 minutes to form a cured film, and a cured film is provided on the production substrate. The TST evaluation substrate.

Next, after mounting a 20 mm square wafer by the C4 method, as a pretreatment, heat treatment at 125° C. for 24 hours, humidity treatment at 60° C. humidity of 60% for 48 hours, and reflow at 260° C. 3 times. The obtained substrate was placed in a thermal cycler for temperature cycling between -65°C and 175°C, and TCT (Thermal Cycle Test) was performed. Furthermore, the appearances at 300 cycles, 600 cycles, and 800 cycles were observed.

◎◎: 1000 cycles or more without abnormality.

◎: 800 cycles or more and no abnormality.

○: 800 cycles and cracks occurred.

Δ: 600 cycles and cracks occurred.

×: 300 cycles and cracks occurred.

*3: PCR-1170H (a carboxyl group-containing resin using a novolac type epoxy resin as a starting material) manufactured by Nippon Kayaku Co., Ltd. (alkali-soluble base equivalent: 656g/eq.)

*4: Epoxy resin B-1 with silsesquioxane skeleton synthesized above (epoxy equivalent: 176 g/eq., 2-functional, softening point: -50°C)

*5: Epiclon N-740 manufactured by DIC Corporation (Novolak-type epoxy resin, epoxy equivalent: 180 g/eq., trifunctional, softening point: 30°C)

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

*7: Epiclon HP-820 manufactured by DIC Corporation (alkanol-type epoxy resin, epoxy equivalent: 225 g/eq., bifunctional, liquid)

*8: Epototo YDC-1312 manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (hydroquinone epoxy resin, epoxy equivalent: 178 g/eq., bifunctional, softening point: 140°C)

*9: Epototo YSLV-80XY manufactured by Nippon Steel & Sumitomo Metal 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 epoxy resin, epoxy equivalent: 475 g/eq., bifunctional, softening point: 64°C)

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

*13: Dicyandiamide

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

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

*16: Irgacure OXE02 (Ethanone, 1-[9-ethyl-6-(2-benzoic acid methyl)-9H-carbazolyl-3-yl]-1-(o-acetone), manufactured by BASF JAPAN oxime)

*17: Surface-treated silica solvent dispersion product E-1 (silicon dioxide having a methacrylic group as a reactive group) (silicon dioxide content of 70% by mass (solid content)) ( Average particle size 600nm) (the value in the table represents the amount of solid content)

*18: Surface-treated silica solvent-dispersed product E-2 (silicon dioxide having epoxy groups as reactive groups) (silicon dioxide content of 68.6% by mass (solid content)) (average Particle size 300nm) (the value in the table represents the amount of solid content)

*19: Admanano YA050C-SV2 (Silicon dioxide with vinyl group as a reactive group) manufactured by Admatex (average particle size: 50 nm)

*20: Admafine SO-C2 manufactured by Admatex (Spherical silica, average particle size 0.5 μm)

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

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

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

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

From the results shown in the above table, it can be seen that the cured products of the curable resin compositions of Examples 1 to 17 of the present invention are excellent in crack resistance. On the other hand, in the cured products of the curable resin compositions of Comparative Examples 1 to 5, the maximum value of Tan δ exceeded 0.15, and crack resistance could not be obtained.

Claims (12)

A curable resin composition containing (A) Alkali-soluble resin, (B) thermosetting components, (C) a compound having an ethylenically unsaturated group, (D) a photopolymerization initiator, and (E) resin composition of surface-treated inorganic filler, It is characterized in that the average particle size of the surface-treated inorganic filler (E) is 100 nm to 1 μm, and it has vinyl properties that can be combined with the (A) alkali-soluble resin, the (B) thermosetting component, and the (C) above. At least any one of the reactive groups in the compound of unsaturated groups reacts, As the above-mentioned (B) thermosetting component, an epoxy resin having an epoxy equivalent of 300 g/eq. or less is contained, The above-mentioned (A) alkali-soluble resin includes any one of the carboxyl group-containing resins described in the following (3), (4), (5) or (8), (3) An epoxy compound having two or more epoxy groups in one molecule and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule are reacted with an unsaturated group-containing monocarboxylic acid, The carboxyl group-containing photosensitive resin obtained by reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride; (4) A reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in one molecule with an alkylene oxide, reacting with an unsaturated group-containing monocarboxylic acid, and reacting the obtained reaction product with a polybasic acid anhydride. Carboxyl-containing photosensitive resin; (5) A compound having two or more phenolic hydroxyl groups in one molecule and a ring The reaction product obtained from the reaction of the carbonate compound is reacted with a monocarboxylic acid containing an unsaturated group, and the resulting reaction product is reacted with a polybasic acid anhydride to obtain a carboxyl group-containing photosensitive resin; (8) A carboxyl group-containing photosensitive resin obtained by adding the carboxyl group-containing resin of the above (3), (4) or (5) to a compound having a cyclic ether group and a (meth)acryloyl group in one molecule; In a cured product with a thickness of 40 μm obtained from the resin composition, when the dynamic viscoelasticity was measured from 25°C to 300°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C/min, the maximum value of Tanδ was 0.15 or less. The curable resin composition of claim 1, wherein, In the carboxyl group-containing resin described in the aforementioned (3), the aforementioned unsaturated group-containing monocarboxylic acid is (meth)acrylic acid, and the aforementioned polybasic acid anhydride is maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and benzene homogenate. Tetraacid anhydride or adipic anhydride, In the carboxyl group-containing resin described in the above (4), the compound having two or more phenolic hydroxyl groups in one molecule is bisphenol A, bisphenol F, bisphenol S, novolac-type phenol resin, poly-p-hydroxybenzene The condensate of ethylene, naphthol and aldehydes or the condensate of dihydroxynaphthalene and aldehydes, the aforementioned alkylene oxide is ethylene oxide or propylene oxide, and the aforementioned unsaturated group-containing monocarboxylic acid is (meth)acrylic acid , In the carboxyl group-containing resin according to (5), the cyclic carbonate compound is ethylene carbonate or propylene carbonate. The curable resin composition according to claim 1, wherein as the epoxy resin having an epoxy equivalent of 300 g/eq. or less, it contains (B-1) Epoxy resins with a softening point of 40°C or lower and a bifunctional or higher; Equivalent ratio (b-1) of the epoxy group (b-1) of the aforementioned (B-1) epoxy resin to the epoxy group (b-2) of the aforementioned (B-2) epoxy resin: (b-2) ) is 3:7~9:1. The curable resin composition according to claim 1, wherein the compounding amount of the compound having an ethylenically unsaturated group (C) is less than 20 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin. The curable resin composition according to claim 1, wherein the blending amount of the (E) surface-treated inorganic filler is 35% by mass or more in the solid content of the curable resin composition. The curable resin composition according to claim 1, wherein when the dynamic viscoelasticity of the cured product is measured from 25°C to 300°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C/min, the storage elastic modulus at 150°C is 1 GPa above, and the change rate of the storage elastic modulus from 25°C to 150°C is within 70%. The curable resin composition according to claim 1, wherein the CTEα2 of the cured product is 110 ppm or less. The curable resin composition according to claim 1, wherein the Tg of the cured product is 160°C or higher. The curable resin composition according to claim 1, which is for forming a solder resist. A dry film characterized by having a resin layer obtained by coating the curable resin composition of claim 1 on a film and drying it. A cured product, which is obtained by curing the curable resin composition according to any one of claims 1 to 9, or the resin layer of the dry film according to claim 10. A printed wiring board is characterized by having the hardened material as claimed in claim 11.

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