TWI745366B - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

The present invention is to provide a curable resin composition or the like that can obtain a cured product excellent in crack resistance when a high-temperature load is applied. The present invention is to provide a curable resin composition, etc., 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 resin composition of a surface-treated inorganic filler, wherein the aforementioned (E) inorganic filler has an average particle diameter of 100 nm to 1 μm, and has the ability to interact with the aforementioned (A) alkali-soluble resin and the aforementioned (B) ) The thermosetting component and the reactive group of at least one reaction among the aforementioned (C) compound having an ethylenically unsaturated group, as the aforementioned (B) thermosetting component, contains an epoxy resin with an epoxy equivalent of 300 g/eq. or less When the dynamic viscoelasticity 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 maximum value of Tanδ 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, a dry film, a cured product, and a printed wiring board.

In recent years, with the rapid advancement of semiconductor components, electronic devices have tended to be lighter, thinner, shorter, smaller, higher performance, and more versatile. 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), etc. In addition, in recent years, FC-BGA (Flip chip. Ball grid array) has also been used as a high-density IC package. In the printed wiring board (also called the package substrate) used in such IC packaging, the SRO (Solder Resist Opening) pitch becomes narrow and is formed close to each other. Therefore, the solder photoresist formed between the SROs becomes longer. Thin and thin, and easy to crack.

In the future, on the other side of the progress of the thin film solder photoresist, the heat generation of the mounted parts tends to increase, so it must be further increased at high temperatures. Resistance to cracking. Particularly, the current density of automotive parts is high, and they are prone to high temperatures, so the premise is that they must be used in an environment where cracks are more likely to occur.

In the past, as a method for improving crack resistance, for example, a photocurable resin composition containing an acid-modified vinyl-containing epoxy resin, an elastomer, a photopolymerization initiator, a diluent, and a hardener has been disclosed (e.g., Patent Literature 1). This patent document 1 discloses that an elastomer improves the crack resistance.

However, only by the above-mentioned means, when the crack resistance is further required in the high temperature state in the future, the result cannot be satisfied.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 11-240930

Here, the 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 For a board, this curable resin composition can obtain a cured product having excellent crack resistance when subjected to a high-temperature load.

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

The stress mainly includes (1) the stress caused by the difference in thermal line expansion (CTE) between the solder photoresist and the surrounding components (copper, substrate, etc.), and (2) the gas (solder photoresist and, (3) The stress (skew) caused by the cross-linking reaction in the solder photoresist caused by the thermal history after mounting. In the past, in order to suppress cracks, solder resists were mixed with elastomers to relax the stress, or the solder resists were made to have a high glass transition temperature (Tg) and low CTE. The stress is effective.

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

Here, the inventors have found that, in addition to the original means to reduce the thermal expansion coefficient of the solder whose thermal expansion coefficient and elastic modulus change due to heat, after hardening, the elastic modulus decreases above Tg. In terms of characteristics, it is necessary to consider the viscoelasticity evaluation of DMA, which is proportional to the displacement speed (viscosity). The change in the viscosity component caused by the DMA is a very important physical property for predicting the characteristics of the 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. Materials with large maximum values of Tanδ peaks (such as materials with the physical properties shown in Figure 1) are used to alleviate the mechanical problems caused by electronic components. For the purpose of sexual pressure, it is suitable for soft and soft components. On the other hand, materials with a small peak value of Tanδ (such as materials with the physical properties shown in Figure 2) are more rigid and temperature resistant in order to resist pressure. Dependence is less.

In addition, the latter method must also be considered for IC packaging in the future, that is, as long as the Tanδ value of DMA is less than 0.15, there will be less viscous components in the cured product. Therefore, the viscous components will be caused by thermal history. Part of the cross-linking reaction progresses, and the cross-linking structure will be looser due to molecular movement near Tg, which can inhibit changes in physical properties. In other words, since the temperature dependence is less, and the physical property changes before and after Tg are less, the stress caused by the physical property changes caused by the high-temperature thermal history can be reduced. Therefore, as long as the Tanδ value of DMA is less than 0.15, not only the stress of (1) above, but the stress suppression of (3) is also effective.

Moreover, 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 by setting the epoxy equivalent of the epoxy resin In the range below the specified value, the stress of (2) is more 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 average particle diameter of the aforementioned (E) surface-treated inorganic filler is 100 nm to 1 μm, and it can be combined with the aforementioned (A) alkali-soluble resin, The aforementioned (B) thermosetting component and the aforementioned (C) tool At least one reactive group in the compound having an ethylenically unsaturated group, as the aforementioned (B) thermosetting component, contains an epoxy resin with an epoxy equivalent of 300 g/eq. or less, and the thickness of the aforementioned resin composition is 40 μm In the cured product, the maximum value of Tanδ is 0.15 or less when the dynamic viscoelasticity 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 curable resin composition of the present invention contains (B-1) a bifunctional or higher epoxy resin with a softening point of 40°C or less and (B-2) a bifunctional or higher epoxy resin with a softening point of 40°C or higher as the aforementioned ring An epoxy resin with an oxygen equivalent of 300 g/eq. or less is preferred.

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

In the curable resin composition of the present invention, the blending amount of the aforementioned (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, the cured product is measured under the conditions of a frequency of 1 Hz and a heating rate of 5°C/min. When dynamic viscoelasticity is measured from 25°C to 300°C, the storage elasticity at 150°C is 1 GPa or more. And the change rate of the storage elasticity 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 aforementioned cured product The Tg is preferably 160°C or higher.

The curable resin composition of the present invention is suitable 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 the present invention has the aforementioned cured product.

According to the present invention, it is possible to provide a curable resin composition capable of obtaining a cured product having excellent crack resistance under high-temperature load, a dry film having a resin layer obtained from the composition, and the composition Or the cured product of the resin layer of the dry film, and the printed wiring board having the cured product.

[Fig. 1] Fig. 1 is an image showing the storage elastic modulus, loss elastic modulus, and Tan δ of a hardened material with a large maximum value of the peak of Tanδ.

[Figure 2] Figure 2 shows images of the storage elastic modulus, loss elastic modulus, and Tan δ of a hardened material with a small maximum value of the peak of Tanδ.

The maximum value of Tanδ of the cured product of the curable resin composition of the present invention at a temperature range of 25 to 300°C is 0.15 or less. As long as it has such physical properties, the temperature of the cured film can be obtained even if exposed to a low temperature to a high temperature. The stability of crack resistance.

And the physical properties of this specification, Tan [delta], etc. cured as long as not particularly limited, about 500mJ / cm ² for the UV irradiation of the resin layer after drying the composition of the resin, further to comprising UV conveyor oven a high-pressure mercury lamp to The physical properties of a cured product with a thickness of 40μm obtained by irradiating with 1J/cm ² exposure light and heating at 160°C for 60 minutes to completely cure the resin layer. In addition, ultraviolet rays are electromagnetic waves with a wavelength of 10 to 400 nm. Tanδ is the value obtained by dividing the loss elasticity measured by the dynamic viscoelasticity measurement by the storage elasticity, that is, it is the loss tangent (=loss elasticity/storage elasticity). In this manual, it is measured by the dynamic viscoelasticity measurement The physical properties such as Tanδ are based on the graphs measured from 25°C to 300°C under the conditions of a frequency of 1 Hz and a heating rate of 5°C/min.

In order to obtain a hardened product with a small Tanδ (=loss elastic modulus/storage elastic modulus), reduce the loss modulus (viscous component) or increase the storage elastic modulus (elastic component). You can do both of them instead. In other words, in the hardened product, instead of increasing the viscous component, it is better to increase the elastic component as much as possible.

The means for setting the maximum value of Tanδ to 0.15 or less is not particularly limited, but the average particle size is 100nm~1μm, and it has the ability to interact with (A) alkali-soluble resin, (B) thermosetting component, and (C) At least one reactive group in the compound of ethylenically unsaturated group has no surface treatment Organic filler, and as the (B) thermosetting component, it is effective to use epoxy resin with an epoxy equivalent of 300 g/eq. or less.

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

In addition, by including epoxy resin with an epoxy equivalent of 300 g/eq. or less as the (B) thermosetting component, the number of cross-linking points with (A) alkali-soluble resin will increase, so the cross-linking density will increase, and it will be able to Reduce unreacted (A) alkali-soluble resin, etc. Therefore, the maximum value of Tanδ becomes smaller, and the cured product does not change rapidly in elastic modulus at a high temperature near 150°C, and the crack resistance is further improved.

Therefore, by curing the composition containing (E) inorganic filler and epoxy resin with epoxy equivalent of 300g/eq. or less as described above, the maximum value of Tanδ of the cured product in the range of 25~300℃ It will be less than 0.15, and stable crack resistance can be obtained. If the maximum value of Tanδ is 0.13 or less, the crack resistance is better.

Furthermore, as described later, even if the blending amount of the compound having an ethylenically unsaturated group (C) is reduced to a small amount, the Tanδ of the cured product can be reduced.

When the maximum value of Tanδ of the cured product is large, if the cured product is exposed to high temperature, the viscosity of the cured product will easily change, and the physical properties will change greatly. However, if the maximum value of Tanδ is less than 0.15, the cured product will change Even in the high temperature state close to the Tg of the hardened material, the viscous component is still There is almost no change, and the change in physical properties is small, and the generation of cracks can be suppressed.

Furthermore, 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 it is preferably 1 GPa or more. More preferably, it is 2 GPa or more. If the storage elastic modulus is above 1 GPa, the resistance of the cured product to the water vapor pressure inside the package will increase, and the crack resistance or insulation reliability will increase.

In addition, in order to obtain crack resistance at high temperature in the past, it is better to change the storage elastic modulus to a large extent for stress absorption.

However, in the curable resin composition of the present invention, on the contrary, the change rate of the storage elastic modulus is reduced, so that it can maintain strength and toughness even at high temperatures, suppress the generation of stress, and suppress the generation of cracks.

In the present invention, the change rate of the storage elasticity is smaller, and the change rate of the storage elasticity 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°C or higher. The higher the Tg, the lower the change in physical properties at high temperatures.

Hereinafter, each component of the curable resin composition of the present invention will be explained. In addition, in this specification, (meth)acrylate refers to the general term of acrylate, methyl acrylate, and mixtures of these. Regarding other similar The performance is the same.

[(A) Alkali-soluble resin]

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

In addition, (A) the weight average molecular weight of the alkali-soluble resin is smaller, the ratio of alkali-soluble groups of the alkali-soluble resin will increase, and the crosslinking density of the cured product will also increase, so it is preferable. (A) When the weight average molecular weight of the alkali-soluble resin is measured by weight average molecular weight (Mw) colloidal permeation chromatography (GPC), it is preferably 10,000 or less in terms of polystyrene.

(A) The 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. Moreover, you may use only the carboxyl group-containing resin which does not have an ethylenic unsaturated group. The ethylenically unsaturated group is preferably acrylic acid, methacrylic acid, or derivatives derived from these.

As specific examples of the carboxyl group-containing resin, there are the compounds (either oligomer or polymer) listed below.

(1) Reaction of a bifunctional or more multifunctional epoxy resin with (meth)acrylic acid to add phthalic anhydride and tetrahydroxide to hydroxyl groups with side chains A carboxyl group-containing photosensitive resin of two-base acid anhydrides such as phthalic anhydride and hexahydrophthalic anhydride. Here, the bifunctional or more multifunctional epoxy resin is preferably a solid.

(2) The polyfunctional epoxy resin in which the hydroxyl group of the bifunctional epoxy resin is further epoxidized with epichlorohydrin is reacted with (meth)acrylic acid, and the resulting hydroxyl group is added to the carboxyl group-containing photosensitive of the 2-base acid anhydride性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 (meth)acrylic acid, etc. The reaction product is obtained by reacting the alcoholic hydroxyl group of the reaction product with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride and other polybasic acid anhydrides. The photosensitive resin containing carboxyl groups.

(4) Make bisphenol A, bisphenol F, bisphenol S, novolac phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxy naphthalene and aldehydes, etc. The reaction product obtained by reacting a compound having two or more phenolic hydroxyl groups in the molecule with alkylene oxide such as ethylene oxide and propylene oxide reacts 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) The 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 A carboxyl group-containing photosensitive tree obtained by reacting the resulting reaction product with a polybasic acid anhydride fat.

(6) Copolymerization of unsaturated carboxylic acids such as (meth)acrylic acid with unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. The obtained carboxyl group-containing photosensitive resin.

(7) The polyfunctional tetracyclic ether resin described below is reacted with dicarboxylic acids such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is added to the carboxyl group of the 2-base acid anhydride Of polyester resin.

(8) A carboxyl group-containing resin such as the above (1) to (7) is added to a carboxyl group-containing photosensitive resin having a compound of a cyclic ether group and a (meth)acryloyl group in one molecule.

As a carboxyl-containing resin having an ethylenically unsaturated group (also called a carboxyl-containing photosensitive resin), it is preferable to have a structure in which the main chain and the side chain of the phenol resin or epoxy resin are separated from the ethylenic unsaturated group . In other words, when an ethylenically unsaturated group is introduced into the side chain, it is preferable to introduce a chain extension structure to create a certain distance between the main chain and the ethylenically unsaturated group. With such a structure, the reactivity of the ethylenically unsaturated groups of the side chain with each other is improved, 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 resin described in (3), (4), (5), and (8) above is preferable.

(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 40 mgKOH/g or more, the alkali development becomes better. In addition, by setting the acid value to 150 mgKOH/g or less, it is possible to easily draw a pattern of a normal cured product. More preferably, it is 50 to 130 mgKOH/g.

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

[(B) Thermal hardening 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 to increase the crosslink 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 oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type 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; Alkylphenol type epoxy resin (such as bisphenol 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; with dicyclopentane Diene skeleton epoxy resin; triphenylmethane type epoxy resin; epoxy resin with silsesquioxane skeleton; glycidyl methacrylate copolymer epoxy resin; cyclohexyl maleimide and shrinkage Glycerol methacrylate copolymerized epoxy resin; epoxy modified polybutadiene rubber derivative; CTBN modified epoxy resin, etc. The epoxy resin can be used individually by 1 type or in combination of 2 or more types. Among these, especially novolak type epoxy resin, bisphenol type epoxy resin, double phenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, naphthalene type epoxy resin , At least one of epoxy resin having a silsesquioxane skeleton and triphenylmethane type epoxy resin is preferable.

As commercial products of epoxy resins with an epoxy equivalent of 300 g/eq. or less, there are EXP7241 (triphenylmethane type epoxy resin) manufactured by DIC Corporation, HP6000 (epoxy resin with naphthyl group), Epiclon N -740 (phenol novolac type epoxy resin), Eptoto YDC-1312 (hydroquinone type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., YSLV-80XY (bisphenol F type epoxy resin), etc.

Since the composition of the present invention can further increase the crosslink density, from the viewpoint of reducing Tanδ, it is preferable to contain two or more types of polyfunctional epoxy resins as the (B) thermosetting component. In this specification, "multifunctional" means bifunctional or more. In addition, the composition of the present invention, as the (B) thermosetting component, preferably contains (B-1) a bifunctional or higher epoxy resin with a softening point of 40°C or less, and contains the (B-1) component, and (B) -2) Mixtures of epoxy resins having a softening point of more than 40°C and bifunctional or higher are preferred. By including (B-1) a bifunctional epoxy resin with a softening point of 40℃ or less, (E) inorganic filler The filler can be highly filled, with low CTE and low Tanδ. In the temperature cycle test, the crack resistance will be improved. Furthermore, by also including (B-2) a bifunctional or higher epoxy resin with a softening point exceeding 40°C, the glass transition temperature (Tg) of the entire curable resin composition can be increased. 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 the value measured according to the method described in JIS K 7234.

(B-1) A bifunctional or higher epoxy resin having a softening point of 40°C or less includes well-known resins. For example, it is preferably a liquid at room temperature. (B-1) Commercial products of bifunctional or higher epoxy resins with a softening point of 40°C or less include, for example, Epikote 834, 828 (manufactured by Mitsubishi Chemical Corporation), and YD-128 (manufactured by Nippon Steel & Sumikin 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 & Sumikin Chemical Co., Ltd.), 830, 835, N-730A ( Bisphenol F type epoxy resin (manufactured by DIC Corporation), ZX-1059 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), a mixture of bisphenol A and bisphenol F, YX-8000, 8034 (manufactured by Mitsubishi Chemical Corporation) ST -3000 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) and other hydrogenated bisphenol A epoxy resins, RE-306CA90 manufactured by Nippon Kayaku Co., Ltd., novolac epoxy resins such as DEN431 and DEN438 manufactured by Dow Chemical Co., Ltd., Alkylphenol type epoxy resin such as Epiclon HP-820 manufactured by DIC.

(B-1) The content of a bifunctional epoxy resin with a softening point of 40°C or less is 1 equivalent to the alkali-soluble group of (A) alkali-soluble resin, and (B-1) a bifunctional epoxy resin with a softening point of 40°C or less Of the above epoxy resin The epoxy group is preferably in the range of 0.2 to 1.8 equivalents. (B-1) The softening point of a bifunctional or higher epoxy resin with a softening point of 40°C or less is preferably -80 to 30°C, more preferably -70 to 20°C. In the high filling of (E) inorganic filler that is effective for reducing Tanδ, if a bifunctional epoxy resin with a softening point of 40°C or less is used, the freedom of compounding design can be broadened and increased Then intensity.

(B-2) Commercial products of bifunctional or higher epoxy resins with a softening point exceeding 40°C include, for example, ICTEP-S (softening point: 110°C) manufactured by Nissan Chemical Co., Ltd., TEPIC-H, N870, DIC HP-7200 (softening point: 60℃), HP-4700 (softening point: 90℃), HP-4710 (softening point: 96℃), EXA-7241 (softening point: 70℃), Mitsubishi Chemical Corporation YX-4000 (softening point: 105℃) manufactured by Nippon Kayaku Co., Ltd. NC-3000L (softening point: 52℃), NC-7000L (softening point: 86℃), CER-3000L (softening point: 93℃) ), EPPN-502H (softening point: 67°C), Eptoto YSLV-80XY (softening point: 80°C) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., EPICLON-N660 (softening point: 61~69°C), Nippon Steel & Sumikin Eptoto YDC-1312 (softening point: 140°C) manufactured by Chemical Corporation, etc.

(B-2) The softening point of a bifunctional or higher epoxy resin with a softening point exceeding 40°C is preferably 50°C or higher, and more preferably 60°C or higher. In addition, (B-2) The upper limit of the softening point of the bifunctional epoxy resin whose softening point exceeds 40°C 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) The blending ratio of a bifunctional epoxy resin with a softening point below 40°C and (B-2) an epoxy resin with a softening point exceeding 40°C is (B-1) a softening point below 40°C The equivalent ratio of epoxy group (b-1) of epoxy resin with more than two functionalities (b-1) and epoxy group (b-2) of epoxy resin (b-2) with softening point of more than 40℃ (b) -1): (b-2) is preferably 3:7-9:1, more preferably 4:6-8:2. When the ratio of epoxy group (b-1) is 3-9, it is possible to balance low Tanδ and high Tg.

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

As a specific example of commercially available epoxy resins having epoxy groups with three or more functionalities, there is a trade name of trifunctional amine phenol epoxy resin "jER-630" (manufactured by Mitsubishi Chemical Corporation), containing trifunctional The brand name of the triazine-based epoxy resin "TEPIC-SP" (manufactured by Nissan Chemical Industry Co., Ltd.), the brand name of the trifunctional aromatic epoxy resin "Techmore VG3101" (manufactured by Printech), and the tetrafunctional aromatic ring The product name of the oxygen resin "GTR-1800" (manufactured by Nippon Kayaku Co., Ltd.), the product name of the modified novolac epoxy resin "EPICLON-N740" (manufactured by DIC Corporation), and the product of dicyclopentadiene epoxy resin The name is "EPICLON-HP7200H-75M" (manufactured by DIC), the trade name of cresol novolac epoxy resin is "EPICLON-N660" (manufactured by DIC), and the trade name of phenol novolak epoxy resin is "jER-152" '' (Mitsubishi Chemical Corporation), one of epoxy resins containing biphenyl skeleton Trade name "NC3000" (manufactured by Nippon Kayaku Co., Ltd.), "NC3000H" (manufactured by Nippon Kayaku Co., Ltd.), "NC3000L" (manufactured by Nippon Kayaku Co., Ltd.), and the trade name of naphthalene type epoxy resin "ESN-175S" (new Nippon Steel & Sumikin Chemical Co., Ltd.), etc.

As the (B) thermosetting component, among the above-mentioned epoxy resins, epoxy resins having a silsesquioxane skeleton can be more suitably used. By blending an epoxy resin with a silsesquioxane skeleton, the proportion of inorganic components in the composition will increase and the viscosity components will decrease. As a result, the maximum value of Tanδ will become smaller, and the hardened product will hardly harden and shrink at high temperatures. Examples of epoxy resins having a silsesquioxane skeleton include silsesquioxane, that is, as long as it is a network polymer _{having a structure of (RSiO 1.5} ) _{n obtained by hydrolyzing a trifunctional silane} Compounds or polyhedral polymers with epoxy-containing groups are not particularly limited. Each silicon of silsesquioxane is bonded with 1.5 oxygen atoms and 1 hydrocarbon group on average.

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 with SiO bonding or an organic group, ^{and at least one of R 1} to R ⁴ is a group with an epoxy group), here, the organic group means a carbon atom The base.

The structure of the aforementioned silsesquioxane is not particularly limited, and silsesquioxanes of known and customary structures such as random structure, trapezoidal structure, complete cage structure, and incomplete cage structure can be used.

There are no particular limitations on the groups having SiO bonding available for R ¹ to R ⁴ , and examples include groups having SiO bonding and aliphatic skeletons, groups having SiO bonding and aromatic skeletons, and groups having SiO bonding. The group of the junction and the hetero atom is preferably within the equivalent range of the above-mentioned thermosetting functional group (epoxy group).

The organic group containing carbon atoms available for R ¹ to R ⁴ is not particularly limited, and examples include aliphatic groups such as methyl groups, aromatic groups such as phenyl groups, and groups having heteroatoms. It is preferably an organic group having 1 to 30 carbon atoms, and it is preferably within the equivalent range 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. Here, the group having an epoxy group is not particularly limited, as long as it is a group having an SiO bond or the organic group has an epoxy group.

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

The curable resin composition of the present invention may also contain epoxy with an epoxy equivalent of 300 g/eq. or less within the 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, isocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, epoxy resins with an epoxy equivalent of more than 300g/eq. can be used. , Tetracyclic ether compounds, episulfide resins, bismaleimide, carbodiimide resins and other well-known compounds. Particularly preferred is a compound having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule. The above-mentioned compound having plural cyclic (thio) ether groups in the molecule is a compound having plural cyclic (thio) ether groups with 3, 4 or 5-membered rings in the molecule, for example, compounds having plural epoxy groups in the molecule, That is, polyfunctional epoxy compounds, compounds having multiple propylene oxide groups in the molecule, that is, polyfunctional tetracyclic ether compounds, compounds having multiple sulfide groups in the molecule, that is, polyfunctional episulfide resins, etc.

[(C) Compounds with ethylenically unsaturated groups]

The curable resin composition of the present invention contains (C) a compound having an ethylenically unsaturated group. (C) As the compound having an ethylenically unsaturated group, a compound having at least one ethylenically unsaturated group in the molecule is preferably used. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc., of a compound having an ethylenically unsaturated group, which is well-known and commonly used, can be used. In addition, the (C) compound having an ethylenically unsaturated group referred to herein does not include (A) an alkali-soluble resin having an ethylenically unsaturated group and (E) a surface-treated inorganic filler.

As the photopolymerizable oligomer, there are unsaturated polyester series Oligomers, (meth)acrylate oligomers, etc. Examples of (meth)acrylate oligomers include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol-type epoxy (meth)acrylic acid. Epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether (meth)acrylate, etc. ) Acrylate, polybutadiene denatured (meth)acrylate, etc.

As the photopolymerizable vinyl monomer, there are well-known and customary ones, such as styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl acetate, vinyl butyrate, or vinyl benzoate, etc. Vinyl esters; ethylene isobutyl ether, ethylene-n-butyl ether, ethylene-t-butyl ether, ethylene-n-dipentyl ether, ethylene isodipentyl ether, ethylene-n-octadecyl ether, ethylene Cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether and other vinyl ethers; acrylamide, methacrylamide, N-methylol acrylamide, N -(Meth)acrylamide such as hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide, etc. Amines; allyl ester compounds such as 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 such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, etc.; Oxyethyl (meth)acrylate, ethoxyethyl (meth) Alkoxyalkylene glycol mono(meth)acrylates such as acrylates; ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentylethylenedi Alcohol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa( Alkylene polyol poly(meth)acrylate such as meth)acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, triethylene glycol ethoxylate Polyoxyalkylene glycol poly(meth)acrylates such as methacrylate, trimethylolpropane tri(meth)acrylate, etc.; neopentyl glycol hydroxypivalate two Poly(meth)acrylates such as (meth)acrylates; isocyanate-type poly(meth)acrylates such as [(meth)acryloxyethyl] isocyanate, etc. These coordinated requirements can be used alone or in combination of two or more.

(C) The blending 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 5-18 parts by mass, and still more preferably 10-15 parts by mass. By reducing the blending amount of the compound having an ethylenically unsaturated group (C), the unreacted compound having an ethylenically unsaturated group in the hardened substance can be reduced, and the elastic modulus of loss (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.

As the photopolymerization initiator, for example, bis-(2,6-dichlorobenzyl)phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-2,5-dimethyl Phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-4-propyl phenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthyl phosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthyl phosphine oxide -(2,6-Dimethoxybenzyl) phenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethylpentyl phosphine oxide, bis- (2,6-Dimethoxybenzyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzyl)-phenylphosphine oxide (BASF JAPAN company Produced by IRGACURE 819) and other bis-amino phosphine oxides; 2,6-dimethoxybenzyl phenylphosphine dioxide, 2,6-dichlorobenzyl phenylphosphine dioxide, 2,4,6-tri Methyl benzalkonium phenyl phenyl phosphonate, 2-benzoic acid methyl phenyl phosphine dioxide, trimethyl ethyl phenyl phenyl phosphonate, 2,4,6-trimethyl benzyl Monophosphine oxides such as phenylphosphine 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-propanyl)-benzyl]phenyl}- 2-Methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one and other hydroxyacetophenones; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n -Benzoins such as propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methyl bis Benzophenones such as benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylamine benzophenone; 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-dimethylaminoacetophenone And other acetophenones; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, Thioxanthones such as 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; scallion, chloroscallion, 2-methyl scallion, 2-ethyl scallion, 2-tert- Butyl scallion, 1-chloro scallion, 2-amino scallion, 2-amino scallion, etc.; acetophenone dimethyl ketal, benzyl dimethyl ketal, etc. Class; Benzoic acid esters such as ethyl-4-aminobenzoic acid dimethyl, 2-(dimethylamine) ethyl benzoate, p-dimethyl benzoic acid ethyl ester; 1,2-octane Dione, 1-[4-(phenylsulfide)-, 2-(O-benzyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl)- 9H-carbazolyl-3-yl]-,1-(O-acetoxime) and other oxime esters; 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.; phenyl sulfide 2-nitrofen, butyroin, anisin ether, azobisisobutyronitrile, tetramethylamine disulfide thiomethionyl Wait. A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, monophosphine oxides and oxime esters are preferred, and high-sensitivity oxime esters are the most preferred. As oxime esters, it is preferable to have one or more oxime ester groups, for example, ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl)-9H-carbazolyl-3 -Radical] -, 1-(O-acetyl oxime) is even more preferred.

The blending amount of the photopolymerization initiator is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the (A) alkali-soluble resin. When it is 0.5 parts by mass or more, the surface hardenability becomes better, and when it is 20 parts by mass or less, halation is unlikely to occur, 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 average particle size of the (E) surface-treated inorganic filler is 100nm~1μm, and it has the ability to interact with (A) alkali A reactive group in which at least one of the soluble resin, (B) the thermosetting component, and (C) the compound having an ethylenically unsaturated group reacts.

The inorganic filler is not particularly limited. Well-known and commonly used fillers, for example, silica, crystalline silica, Noibble clay, aluminum hydroxide, glass powder, mica, clay, magnesium carbonate, and 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, zinc bloom, etc. Among them, silicon dioxide is preferable because the surface area becomes smaller and the stress is dispersed throughout the entire body. Therefore, it is difficult to become the starting point of cracks, and because of its excellent resolution, spherical silicon dioxide is even more preferable.

(E) The reactive group of the surface-treated inorganic filler includes, for example, a (meth)acrylic 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, a propylene oxide 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, an sulfonium group, a phosphoric acid group, and the like.

Examples of the basic group include an amino group, an amide group, and an ammonium group.

(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, it has excellent reactivity with (A) alkali-soluble resin. If it is a (meth)acryloyl group or vinyl group , The reactivity with the ethylenic unsaturated group of (A) alkali-soluble resin is superior.

The method of introducing the aforementioned reactive group into the inorganic filler is not particularly limited, as long as it is introduced using a known and customary method, as long as it is a surface treatment agent having the aforementioned reactive group, for example, a coupling agent having the aforementioned reactive group Wait to treat the surface of the inorganic filler.

The surface treatment as an inorganic filler is preferably a surface treatment with a coupling agent. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. can be used. Among them, silane coupling agents are preferred.

As the silane coupling agent capable of introducing the aforementioned reactive group into the inorganic filler, there are silane coupling agents 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. Among them, a silane coupling agent, a silane coupling agent having a carboxyl group, etc., is preferably a silane coupling agent having at least any one of a (meth)acrylic group and a vinyl group.

(E) The surface-treated inorganic filler can be blended into the curable resin composition of the present invention in a surface-treated state, and the surface-untreated inorganic filler and surface treatment agent can also be blended separately. In the composition, the inorganic filler is surface-treated, but it is preferable to pre-blended the inorganic filler after the surface treatment. By pre-blending the inorganic filler after the surface treatment, it can prevent the remaining surface treatment from being consumed in the separate blending The resistance to cracks caused by the surface treatment agent is reduced. For pre-surface treatment, it is better to mix the pre-dispersion of the inorganic filler in a solvent or resin component. The inorganic filler after the surface treatment is pre-dispersed in the solvent, and then the pre-dispersion is mixed into the composition. Or, it is better to mix the preliminary dispersion liquid into the composition after fully performing surface treatment when the inorganic filler with untreated surface is pre-dispersed in the solvent.

(E) The average particle size of the surface-treated inorganic filler is preferably 100 to 800 nm, more preferably 100 to 700 nm, and even more preferably 200 to 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 the primary particles, but also the average particle diameter (D50) including the particle diameter of the secondary particles (agglomerates). The average particle diameter can be determined by a laser diffraction particle diameter distribution measuring device. As a measuring device for the laser diffraction method, there is a Nanotrac wave manufactured by Nikkiso Co., Ltd., and the like.

(E) The more the surface-treated inorganic fillers are blended, the more the storage elasticity increases, the Tanδ will become smaller, and the hardened material is harder to swell, so (E) the surface-treated inorganic fillers blended It is preferable that it is 35% by mass or more of the total solid content of the curable resin composition. More preferably, it is 38 to 80% by mass.

(Thermal hardening catalyst)

The curable resin composition of the present invention preferably contains a thermosetting catalyst. As such a thermosetting catalyst, there are, for example, 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-di Amine compounds such as methylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, hydrazine compounds such as dihydrazine adipate and dihydrazine sebacate; triphenylphosphine, etc. The phosphorus compounds and so on. In addition, guanamine, acetguanamine, benzoguanamine, melamine, 2,4-diamine-6-methacrylate oxyethyl-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-methacrylate oxyethyl-S-triazabenzene. For the S-triazabenzene derivatives such as isocyanuric acid adducts, it is preferable to use a compound that can also function as an adhesion imparting agent in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is preferably 0.05 to 20 parts by mass, and 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 can contain a curing agent. Examples of hardeners include phenol resins, polycarboxylic acids and their anhydrides, cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. A curing 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 coloring agent, known colors such as red, blue, green, yellow, black, and white can be used The agent may be any of pigments, dyes, and pigments. However, from the viewpoint of reducing the environmental load and the impact on the human body, it is better not to contain halogen.

The addition amount of the coloring agent is not particularly limited, but it is preferably 10 parts by mass or less relative to 100 parts by mass of the (A) alkali-soluble resin, and particularly preferably a sufficient amount in a ratio of 0.1-7 parts by mass.

(Organic solvents)

The curable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition or adjusting the viscosity when it is applied to a substrate or a carrier film. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone can be used; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene; siloxu, methyl siloxu, butyl siloxu, and carbamide 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, siloxol acetate, butyl siloxol acetate, carbitol acetate, butyl carbitol acetate, propylene glycol Monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, solvent naphtha, etc. And other well-known and customary organic solvents. These organic solvents can be used alone or in combination of two or more kinds.

(Other optional ingredients)

Furthermore, in the curable resin composition of the present invention, other additives known and commonly used in the field of electronic materials may be blended. Add as other Agents include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, anti-charge agents, anti-aging agents, and antibacterial agents. Anti-mold agent, defoamer, leveling agent, tackifier, adhesion imparting agent, thixotropy imparting agent, light start aid, sensitizer, thermoplastic resin, organic filler, release agent, surface treatment agent , Dispersants, dispersing aids, surface modifiers, stabilizers, phosphors, AB type or ABA type block copolymers, etc.

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

Next, the dry film of the present invention has a resin layer obtained by coating and drying the curable resin composition of the present invention on a carrier film. When forming a dry film, first, the curable resin composition of the present invention is diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, and then used with a chipped wheel coater, knife coater, slit coater, bar coater, Extrusion coater, reverse coater, transfer roller coater, gravure coater, spray coater, etc., coat the carrier film to a uniform thickness. After that, the coated composition is usually dried at a temperature of 40 to 130° C. for 1 to 30 minutes, thereby forming a resin layer. The coating film thickness is not particularly limited, but the film thickness after drying is generally 3 to 150 μm, and it is preferably appropriately selected in the range of 5 to 60 μm.

As the carrier film, there is a plastic film. For example, polyester film such as polyethylene terephthalate (PET), polyimide film, polyimide film, polypropylene film, polystyrene can be used. Film etc. There are no special restrictions on the thickness of the carrier film, generally 10~ It is appropriately selected within the range of 150 μm. More preferably, it is in the range of 15 to 130 μm.

After the resin layer made of the curable resin composition of the present invention is formed on the carrier film, for the purpose of preventing dust from adhering to the surface of the resin layer, a cover film that can be peeled off on the surface area of the resin layer is preferable. As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. As the cover film, when the cover film is peeled off, it should just be smaller than the adhesive force between the resin layer and the carrier film.

Furthermore, in the present invention, the curable resin composition of the present invention may be coated on the above-mentioned cover film and dried to form a resin layer, and a carrier film may be laminated on the surface. That is, when a dry film is produced in the present invention, as the film to which the curable resin composition of the present invention is applied, either a carrier film or a cover film may be used.

The printed wiring board of the present invention has the curable resin composition of the present invention or a cured product obtained from a 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 immersion coating method, flow coating method, and roll coating method. After coating on the substrate by methods such as rod coating method, screen printing method, screen coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporarily dried) at a temperature of 60~100°C to form Non-sticky resin layer. And, when it is a dry film. After the resin layer is brought into contact with the substrate by a laminating machine or the like to be bonded to the substrate, the carrier film is peeled off to form a resin layer on the substrate.

As the above-mentioned substrates, in addition to printed wiring boards or flexible printed wiring boards with circuits formed in advance with copper, etc., there are also paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/ Non-woven epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, use fluororesin. Polyethylene. Poly(phenylene oxide), poly(phenylene oxide). Cyanate esters and other high-frequency circuits are made of copper laminates and other materials, and can include copper laminates of all grades (FR-4, etc.). In addition, there are metal substrates, polyimide films, and PET films. , Polyethylene naphthalate (PEN) film, glass substrate, ceramic substrate, wafer board, etc.

The volatilization drying performed after coating the curable resin composition of the present invention can use 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 nozzle to the support) are carried out.

After the resin layer is formed on the printed wiring board, through a photomask with a specific pattern, selectively exposed by active energy rays, the unexposed area is exposed with a diluted alkaline aqueous solution (for example, 0.3 to 3% by mass aqueous soda solution) Like, the pattern of the hardened object is formed. Furthermore, the cured product is irradiated with active energy rays and then heated and cured (for example, 100 to 220°C), or heated and cured and then irradiated with active energy rays, or only heated and cured at the final stage of curing (this curing), thereby forming dense A cured film with excellent adhesion and hardness.

As the exposure machine used for the above-mentioned active energy ray irradiation, as long as it is equipped with a high-pressure mercury bulb, ultra-high pressure mercury bulb, metal halide bulb, mercury short-arc bulb, etc., and irradiates ultraviolet rays in the range of 350 to 450 nm. Furthermore, it is also possible to use a direct drawing device (for example, a laser direct imaging device that draws an image with a direct laser using CAD data from a computer). As the bulb light source or laser light source of the direct drawing machine, it can also have the maximum wavelength in the range of 350~450nm. The amount of exposure used for image formation will vary depending on the film thickness, etc., but it is generally 10~1000mJ/cm ² , and preferably can be set in the range of ^{20~800mJ/cm 2.}

As the above-mentioned development method, immersion method, shower method, spray method, brushing method, etc. can be used. As the developer solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. can be used. Alkaline aqueous solutions of ammonia, amines, etc.

The curable resin composition of the present invention is suitably used when forming a cured film on a printed wiring board, when forming a permanent film, and even more suitably when 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 that require high reliability and fine pitch, such as package substrates, especially for permanent coatings (especially solder photoresists) for FC-BGA. In particular, with the curable resin composition of the present invention, it is possible to obtain a cured product excellent in crack resistance when a high-temperature load is applied, so it is suitable for applications exposed to high-temperature conditions such as automotive applications.

Example

Hereinafter, the present invention will be explained in further detail using examples, but the present invention is not limited to the following examples. In addition, in the following, "parts" and "%" are all quality standards as long as they are not particularly limited.

[Synthesis of Alkali-soluble Resin A-1]

In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, 119.4 parts of novolak type cresol resin (trade name "Shownor CRG951", manufactured by Showa Polymer Corporation, OH equivalent: 119.4) is introduced, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were replaced with nitrogen in the system while stirring, and the temperature was increased by heating. Next, 63.8 parts of propylene oxide was slowly dropped, and it was made to react at ^{125-132 degreeC at 0-4.8 kg/cm<2> for 16 hours.} After cooling to room temperature, 1.56 parts of 89% phosphoric acid was added to the reaction solution and mixed, potassium hydroxide was neutralized to obtain 62.1% non-volatile matter, and the hydroxyl value was 182.2mgKOH/g (307.9g/eq.) Propylene oxide reaction solution of novolac type cresol resin. This is the average 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.

The resulting novolak-type cresol resin containing 293.0 parts of propylene oxide reaction solution, 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 mixer, a thermometer, and an air blowing tube In the medium, air was blown in at a rate of 10 ml/min, and the reaction was carried out at 110°C for 12 hours while stirring. The water produced by the reaction was used as an azeotropic mixture with toluene, and 12.6 parts of water was distilled out. After that, it was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, followed by washing with water. After that, the toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the obtained novolac type acrylate resin solution and triphenyl 1.22 parts of phosphine is introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air is blown in at a speed of 10ml/min, while stirring, slowly add 60.8 parts of tetrahydrophthalic anhydride to 95~101 It was allowed to react at °C for 6 hours, and then taken out after cooling. In this way, a solution of carboxyl group-containing photosensitive resin A-1 with a non-volatile content of 65% and a solid acid value of 87.7 mgKOH/g was obtained.

[Synthesis of Alkali-soluble Resin A-2]

In 700 g of diethylene glycol monoethyl ether acetate, 1070 g of n-cresol novolac type epoxy resin (manufactured by DIC, EPICLON N-695, softening point 95°C, epoxy equivalent 214, average reactive base number 7.6) was placed in 700 g of diethylene glycol monoethyl ether acetate. (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, heated to 100°C and stirred, and dissolved uniformly.

Next, 4.3 g of triphenylphosphine was put in, and after heating to 110° C. to react for 2 hours, 1.6 g of triphenyl phosphine was further added, and the temperature was raised to 120° C. and the reaction was further performed 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 into the obtained reaction liquid, and the reaction was carried out at 115° C. for 4 hours to obtain a carboxyl group-containing photosensitive resin solution (A-2).

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

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

Put 90.0 parts of γ-glycidoxypropyltrimethoxysilane, 3.0 parts of phenyltrimethoxysilane, 2.0 parts of methyltrimethoxysilane, and 93 parts of methyl isobutyl ketone into the reaction vessel, and raise the temperature to 80°C . After the temperature was raised, 21.6 parts of a 0.1% by weight potassium hydroxide aqueous solution was dropped continuously for 30 minutes. After the dripping, the generated methanol was removed and reacted at 80°C for 5 hours. After the reaction is over, repeated washing with water until the washing liquid becomes neutral. Next, by removing the solvent under reduced pressure, 69 parts of epoxy resin 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 2,200.

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

70 g of spherical silicon dioxide (SFP-30M manufactured by Denka, 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 KBM-503 manufactured by Chemical Industry Co., Ltd.) 2 g was uniformly dispersed to obtain silica solvent dispersion E-1.

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

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

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

The above resin solution (varnish) is blended with the various ingredients shown in Tables 1 to 3 in the proportions (parts by mass) shown in Tables 1 to 3, pre-mixed with a mixer, and then mixed with 3 rolling mills. Prepare a curable resin composition.

<Production of Dry Film>

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

<Production of Hardened Coating Film>

On the low-profile copper foil, peel off the polyethylene film from the photosensitive dry film obtained as described above, paste the photosensitive resin layer of the photosensitive dry film on the surface of the copper foil, and then use a vacuum laminator (Meiji Seisakusho Co., Ltd. MVLP-500), heating the laminate under the conditions of pressure: 0.8MPa, 70°C, 1 minute, and vacuum: 133.3Pa to make the substrate and the photosensitive resin layer adhere to each other.

Next, use an exposure device equipped with a high-pressure mercury lamp (short arc bulb) to expose on the photosensitive dry film (exposure amount: 400~600mJ/cm ² ), and then peel off the polyethylene terephthalate film from the photosensitive dry film , The photosensitive resin layer is exposed. After that, a 1% by weight Na ₂ CO ₃ aqueous solution was used to develop images at 30° C. and a spray pressure of 2 kg/cm ² for 60 seconds to form a resin layer with a specific photoresist pattern. Then, after irradiating the resin layer with a UV conveyor belt furnace equipped with a high-pressure mercury lamp with an ^{exposure of 1 J/cm 2} , it was heated at 160° C. for 60 minutes to completely harden the resin layer to produce a hardened coating film.

<Evaluation of Tanδ, Tg, and Storage Elasticity>

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

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

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

<CTE Evaluation>

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

<Crack resistance (TCT resistance)>

Chemically polish the surface of the substrate (50mm×50mm×0.4mmt) connected to the circuit of C4 with a 250μm uneven pitch, peel off the polyethylene film from the photosensitive dry film obtained above, and bond it on the side that has been polished. The photosensitive resin layer of the photosensitive dry film is then heated using a vacuum laminator (MVLP-500 manufactured by Meiji Seisakusho Co., Ltd.) under the conditions of pressure: 0.8MPa, 70°C, 1 minute, and vacuum: 133.3Pa Laminates make the substrate and the photosensitive resin layer adhere to each other. Next, using an exposure device equipped with a high-pressure mercury lamp (short arc bulb), through an exposure mask with a negative pattern with a diameter of 70 μm, the photosensitive dry film is exposed, and the polyethylene terephthalate is peeled off from the photosensitive dry film. The formate film exposes the photosensitive resin layer. After that, a 1% by weight Na ₂ CO ₃ aqueous solution was used to develop images at 30° C. and a spray pressure of 2 kg/cm ² for 60 seconds to form a resin layer with a specific photoresist pattern. Then, after irradiating the resin layer with a UV conveyor belt furnace equipped with a high-pressure mercury lamp with an ^{exposure of 1J/cm 2,} it is heated at 160°C for 60 minutes to completely harden the resin layer to form a hardened film, and a hardened film is set on the substrate. The TST evaluation board.

Then, after mounting a 20mm square wafer by the C4 method, as a pre-treatment, heat treatment at 125°C for 24 hours, 60°C humidity 60% humidification treatment for 48 hours, and reflow at 260°C 3 times. Put the obtained substrate into a thermal cycler that performs a temperature cycle between -65°C and 175°C, and perform TCT (Thermal Cycle Test). Also, observe the appearance at 300 cycles, 600 cycles, and 800 cycles.

◎◎: 1000 cycles or more without abnormality.

◎: 800 cycles or more without abnormality.

○: 800 cycles and cracks occurred.

△: 600 cycles and cracks occurred.

×: 300 cycles and cracks occurred.

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

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

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

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

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

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

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

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

*9: Eptoto YSLV-80XY manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (bisphenol F epoxy resin, epoxy equivalent: 195 g/eq., bifunctional, softening point: 80°C)

*10: Epiclon 152 manufactured by DIC Corporation (Tetrabromobisphenol A epoxy resin, epoxy equivalent: 360g/eq., bifunctional, softening point: 56~66°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-dihydroxymethylimidazole) 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 (Ethyl ketone, 1-[9-ethyl-6-(2-benzoic acid methyl)-9H-carbazolyl-3-yl]-1-(o-acetyl) manufactured by BASF JAPAN Oxime)

*17: Silicon dioxide solvent dispersion product E-1 (silicon dioxide with a methacrylic group as a reactive group) (silicon dioxide content 70% by mass (solid content)) with the surface treatment adjusted above ( (Average particle size 600nm) (The value in the table indicates the amount of solid content)

*18: Silicon dioxide solvent dispersion product E-2 (silicon dioxide with epoxy group as a reactive group) (silica content 68.6 mass% (solid content)) with the above-mentioned adjusted surface treatment (average (Particle size 300nm) (the value in the table indicates the amount of solid content)

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

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

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

*22: NC-3000L manufactured by Nippon Kayaku Co., Ltd. (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: 168g/eq., trifunctional, softening point: 70°C),

*24: EPICLON-N660 manufactured by DIC Corporation (cresol novolac epoxy resin, epoxy equivalent: 210g/eq., bifunctional, softening point: 61~69°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 have excellent crack resistance. In contrast, in the cured products of the curable resin compositions of Comparative Examples 1 to 5, the maximum value of Tanδ exceeds 0.15, and crack resistance cannot be obtained.

Claims (11)

A curable resin composition containing (A) an alkali-soluble resin, (B) a thermosetting component, (C) a compound having an ethylenically unsaturated group, (D) a photopolymerization initiator, and (E) The resin composition of the surface-treated inorganic filler is characterized in that the average particle diameter of the aforementioned (E) surface-treated inorganic filler is 100nm~1μm, and it can interact with the aforementioned (A) alkali-soluble resin and the aforementioned (B) The thermosetting component and the reactive group of at least one of the aforementioned (C) compound having an ethylenically unsaturated group, as the aforementioned (B) thermosetting component, contains an epoxy resin with an epoxy equivalent of 300 g/eq. or less, And as the aforementioned (B) thermosetting component, it contains (B-1) a bifunctional or more epoxy resin with a softening point of 40°C or less and (B-2) a bifunctional or more epoxy resin with a softening point of more than 40°C. (B-1) Equivalent ratio of epoxy group (b-1) of epoxy resin and epoxy group (b-2) of aforementioned (B-2) epoxy resin (b-1): (b-2) It is 3:7~9:1. When measuring the dynamic viscoelasticity from 25°C to 300°C under the conditions of 1Hz frequency and 5°C/min heating rate in a cured product with a thickness of 40μm obtained from the aforementioned resin composition , The maximum value of Tanδ is 0.15 or less. The curable resin composition of claim 1, wherein the epoxy resin with an epoxy equivalent of 300g/eq. or less contains (B-1) a softening point of 40°C or less The following epoxy resins with more than two functions and (B-2) epoxy resins with more than two functions whose softening point exceeds 40°C. The curable resin composition of claim 1, wherein the blending 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 alkali-soluble resin (A). The curable resin composition of claim 1, wherein the blending amount of the aforementioned (E) surface-treated inorganic filler is 35% by mass or more in the solid content of the curable resin composition. Such as the curable resin composition of 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 elasticity at 150°C is 1 GPa Above, and the change rate of storage elasticity from 25℃~150℃ is within 70%. The curable resin composition of claim 1, wherein the CTEα2 of the cured product is 110 ppm or less. The curable resin composition of claim 1, wherein the Tg of the cured product is 160°C or higher. The curable resin composition of claim 1, which is used 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 the film and drying it. A cured product characterized by curing the curable resin composition of any one of claims 1 to 8, or the resin layer of the dry film of claim 9 Income. A printed wiring board characterized by having a cured product as claimed in claim 10.

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