TW202007726A - Resin composition having excellent viscosity stability, high adhesion strength and low dielectric loss tangent - Google Patents

Abstract

An object of the present invention is to provide a resin composition which is capable of obtaining excellent viscosity stability of a resin varnish, has high adhesion strength to a copper foil after a HAST test, and can obtain a cured product having a low dielectric loss tangent; a resin sheet containing the resin composition; a printed wiring board provided with an insulating layer formed by using the resin composition; and a semiconductor device. The solution of the present invention is a resin composition comprises (A) a fluorine-containing epoxy resin, (B) a curing agent, (C) a styrene-based elastomer, and (D) a resin having a radically polymerizable unsaturated group.

Description

Resin composition

The present invention relates to a resin composition. Furthermore, it is related to the resin sheet containing this resin composition, a printed wiring board, and a semiconductor device.

As a manufacturing technique of a printed wiring board, a manufacturing method of a build-up method in which an insulating layer and a conductor layer are alternately stacked on an inner layer circuit board is known. In recent years, the insulating layer has become an insulating layer that seeks to reduce the loss of electrical signals below a high frequency and seek a low dielectric tangent.

As a resin composition forming such an insulating layer, for example, Patent Document 1 describes a resin composition comprising (A) a thermosetting resin having a styrene group at the end and a molecular weight of 800 to 1500, (B) The liquid epoxy resin, (C) styrene-based thermoplastic elastomer, (D) filler and (E) hardener, (D) component is 30 to 70 parts by mass with respect to 100 parts by mass of the resin composition. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2016-147945

[Problem to be solved by invention]

In order to obtain an insulating layer with a low dielectric tangent, the present inventors conducted research on a resin composition containing a radical polymerizable compound of the entire low-polarized resin composition. As a result, it was found that the compatibility between the copper foil after the environmental test (HAST test) in a high-temperature and high-humidity environment was deteriorated by the radical polymerizable compound contained in the resin composition and the compatibility of the epoxy resin and the like deteriorated New subject of strength degradation. In addition, it was also found that due to the deterioration of the compatibility, when the resin varnish of the dissolved resin composition is stored in the organic solvent, it changes into a gel to increase the viscosity, that is, the viscosity stability of the resin varnish is deteriorated, and it is brand new when producing resin sheets. Subject.

The subject of the present invention is to provide a resin composition that can obtain a cured product of a resin varnish that has excellent viscosity stability, high adhesion strength with copper foil after HAST test, and low dielectric tangent; resin containing the resin composition A sheet; a printed wiring board and a semiconductor device provided with an insulating layer formed using the resin composition. [Means to solve the problem]

As a result of intensive research to solve the aforementioned problems, the inventors found that in addition to (D) a resin having a radical polymerizable unsaturated group, by combining (A) a fluorine-containing epoxy resin, (B) a hardener and (C) The resin composition of the styrene-based elastomer can solve the aforementioned problems and finally complete the present invention. That is, the present invention includes the following content.

[1] A resin composition comprising: (A) fluorine-containing epoxy resin, (B) Hardener, (C) Styrene elastomer and (D) A resin having a radical polymerizable unsaturated group. [2] The resin composition according to [1], wherein when the resin component in the resin composition is set to 100% by mass, the content of the component (C) is 0.5% by mass or more and 18% by mass or less. [3] The resin composition according to [1] or [2], wherein when the (C) component is defined as 100% by mass, the content of the styrene unit in the (C) component includes 61% by mass or more . [4] The resin composition according to any one of [1] to [3], wherein the component (D) contains at least 1 selected from the group consisting of vinyl phenyl, acryloyl and methacryloyl Species. [5] The resin composition according to any one of [1] to [4], wherein the number average molecular weight of the component (D) is 3000 or less. [6] The resin composition as described in any one of [1] to [5], wherein, when the non-volatile component in the resin composition is defined as 100% by mass, the content of the component (B) is 1% by mass 15% by mass or more. [7] The resin composition as described in any one of [1] to [6], which further contains (E) an inorganic filler. [8] The resin composition as described in [7], wherein the content of the component (E) is 50% by mass or more when the nonvolatile component in the resin composition is set to 100% by mass. [9] The resin composition as described in any one of [1] to [8], which is for forming an insulating layer. [10] The resin composition as described in any one of [1] to [9], which is used to form an insulating layer for forming a conductor layer. [11] The resin composition as described in any one of [1] to [10], which is used to form an insulating layer for forming a conductor layer by sputtering or metal foil. [12] The resin composition as described in any one of [1] to [11], which is for forming an insulating layer having a through hole having a top diameter of 45 μm or less. [13] The resin composition as described in any one of [1] to [12], which is for forming an insulating layer having a thickness of 20 μm or less. [14] A resin sheet comprising a support and a resin composition layer provided on the support and containing the resin composition as described in any one of [1] to [13]. [15] A printed wiring board comprising an insulating layer formed by a cured product of the resin composition as described in any one of [1] to [13]. [16] A semiconductor device including the printed wiring board as described in [15]. [Effect of the invention]

According to the present invention, it is possible to provide a resin composition that can obtain a cured product of a resin varnish that has excellent viscosity stability, high adhesion strength with copper foil after HAST test, and low dielectric tangent; A resin sheet; a printed wiring board and a semiconductor device provided with an insulating layer formed using the resin composition.

Hereinafter, the embodiments and the examples will be shown, and the present invention will be described in detail. However, the present invention is not limited to the embodiments and examples listed below, and can be arbitrarily modified and implemented without departing from the scope of the patent application of the present invention and its equivalent scope.

[Resin composition] The resin composition of the present invention contains (A) a fluorine-containing epoxy resin, (B) a curing agent, (C) a styrene elastomer, and (D) a resin having a radical polymerizable unsaturated group. With such a resin composition, it becomes a hardened product that can obtain a resin varnish with excellent viscosity stability, high adhesion strength with copper foil after HAST test, and low dielectric tangent. Furthermore, by using such a resin composition, generally, even before the HAST test, the adhesion strength with the copper foil can be increased, and the peel strength with the plated conductor layer can also be increased.

The resin composition may be combined with the components (A) to (D), and further contains arbitrary components. Examples of arbitrary components include (E) inorganic fillers, (F) hardening accelerators, (G) polymerization initiators, (H) epoxy resins, and (I) other additives. Hereinafter, each component contained in the resin composition will be described in detail.

＜(A) Fluorine-containing epoxy resin＞ The resin composition contains a fluorine-containing epoxy resin as the (A) component. By containing (A) a fluorine-containing epoxy resin in the resin composition, it can be obtained that the resin varnish has excellent viscosity stability, high adhesion strength with copper foil after HAST test, and low dielectric tangent hardening Thing.

As (A) a fluorine-containing epoxy resin, an epoxy resin containing one or more fluorine atoms per molecule can be used. The number of fluorine atoms per molecule is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more and 5 or more. Although the upper limit is not particularly limited, it may be 10 or less.

The resin composition as (A) the fluorine-containing epoxy resin is preferably a resin having two or more epoxy groups in one molecule. From the viewpoint of obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups per molecule with respect to (A) 100% by mass of the non-volatile content of the fluorine-containing epoxy resin It is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

(A) Among the fluorine-containing epoxy resins, there are fluorine-containing epoxy resins that are liquid at a temperature of 20°C and fluorine-containing epoxy resins that are solid at a temperature of 20°C. The resin composition as (A) a fluorine-containing epoxy resin may be a liquid-containing fluorine-containing epoxy resin, a solid-state fluorine-containing epoxy resin only, or a combination containing a liquid The fluorine-containing epoxy resin and the solid fluorine-containing epoxy resin.

Further, (A) the fluorine-containing epoxy resin is preferably an aromatic fluorine-containing epoxy resin from the viewpoint of obtaining the desired effect of the present invention.

(A) Specific examples of the fluorine-containing epoxy resin include bisphenol AF epoxy resin, perfluoroalkyl epoxy resin, and the like. Among them, from the viewpoint of obtaining the desired effect of the present invention, a bisphenol AF epoxy resin is preferred. These fluorine-containing epoxy resins can be used alone or in combination of two or more.

(A) A commercially available product can be used for the fluorine-containing epoxy resin, and examples thereof include "YL7760" (bisphenol AF epoxy resin) manufactured by Mitsubishi Chemical Corporation.

(A) The epoxy equivalent of the fluorine-containing epoxy resin is preferably 50 g/eq. to 5000 g/eq., more preferably 50 g/eq. to 3000 g/eq., and even more preferably 80 g/eq. to 2000 g. /eq., and even more preferably 110g/eq. to 1000g/eq. By being in this range, the cross-link density of the cured product of the resin composition layer becomes sufficient, and an insulating layer with a small surface roughness can be brought. Epoxy equivalent is the mass of epoxy resin containing 1 equivalent of epoxy group. This epoxy equivalent can be measured in accordance with JIS K7236.

(A) The weight average molecular weight (Mw) of the fluorine-containing epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 from the viewpoint of remarkably obtaining the desired effect of the present invention. ~1500. The weight-average molecular weight of the resin can be measured as a value converted to polystyrene by gel permeation chromatography (GPC).

(A) The content of the fluorine-containing epoxy resin, from the viewpoint of obtaining a resin varnish with excellent viscosity stability, high adhesion strength to the copper foil after the HAST test, and a low dielectric tangent hardened product, will be The nonvolatile content in the resin composition is set to 100% by mass, preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more. (A) The upper limit of the content of the fluorine-containing epoxy resin is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. the following. In addition, in the present invention, the content of each component in the resin composition is a value where the non-volatile component in the resin composition is set to 100% by mass unless otherwise stated.

＜(B) Hardener＞ The resin composition system contains a hardener as the (B) component. (B) The hardener usually has a function of reacting with (A) the fluorine-containing epoxy resin to harden the resin composition.

Examples of the (B) hardener include active ester hardeners, phenol hardeners, naphthol hardeners, benzoxazine hardeners, cyanate ester hardeners, and carbodiimide hardeners. Amine hardeners, anhydride hardeners, etc. (B) One type of hardener may be used alone, or two or more types may be used in combination.

As an active ester hardener, it can be used for compounds having one or more active ester groups in one molecule. Among them, as the active ester-based hardener, phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more highly reactive esters in one molecule are preferred. Based compounds. The active ester-based hardener is preferably obtained by condensation reaction of a carboxylic acid compound and/or thiocarboxylic acid compound with a hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, active ester hardeners derived from carboxylic acid compounds and hydroxyl compounds are preferred, and active ester systems derived from carboxylic acid compounds and phenol compounds and/or naphthol compounds are more preferred. hardener.

Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methyl alcohol Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene diphenol Compounds, phenolic novolac, etc. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Preferred specific examples of the active ester-based hardener include active ester-based hardeners containing a dicyclopentadiene-type diphenol structure, active ester-based hardeners containing a naphthalene structure, and phenol novolac acetylates. Active ester-based hardener, active ester-based hardener containing phenol novolac benzoate. Among them, more preferred are active ester-based hardeners containing a naphthalene structure and active ester-based hardeners containing a dicyclopentadiene-type diphenol structure. The so-called "dicyclopentadiene diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentyl-phenylene.

As a commercially available product of an active ester hardener, examples of the active ester hardener including a dicyclopentadiene diphenol structure include "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", " "HPC8000H-65TM", "EXB8000L-65TM", "EXB8150-65T" (manufactured by DIC); examples of active ester-based hardeners containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC); as containing phenol novolac The active ester-based hardener of the acetal compound of the varnish can be exemplified by "DC808" (manufactured by Mitsubishi Chemical Corporation); as the active ester-based hardener of the benzoyl phenol compound containing phenol novolac, the "YLH1026" (Mitsubishi Chemical Company Manufactured); as active ester-based hardeners containing phenol novolak acetyl compounds, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester-based hardeners containing phenol novolak benzoyl compounds. "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation); etc.

As the phenol-based hardener and the naphthol-based hardener, those having a novolac structure are preferred from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based hardener is preferable, and a phenol-based hardener containing a triazine skeleton is more preferable.

Specific examples of the phenol-based hardener and naphthol-based hardener include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals; "NHN" manufactured by Nippon Kayaku Co., Ltd. , "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. ; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation; etc.

Specific examples of the benzoxazine-based hardener include "ODA-BOZ" manufactured by JFE Chemical Company, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), and 4,4′- Methylene bis (2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) methane, 1,3 -Bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl) sulfide and bis(4-cyanate phenyl) ether, etc. 2-functional cyanate resin; multifunctional cyanate resins derived from phenol novolak and cresol novolak; some of these cyanate resins are triazineized prepolymers; etc. Specific examples of the cyanate ester-based hardener include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate ester resin) manufactured by Lonza Japan, and "ULL-950S" (polyfunctional cyanate Ester ester resin), "BA230", "BA230S75" (prepolymer of trimerized terpolymer that becomes part or all of bisphenol A dicyanate), etc.

Specific examples of carbodiimide-based hardeners include "V-03", "V-05", "V-07", and "V-09" manufactured by Nisshinbo Chemical Co., Ltd.; and Stabaczole ("Stabaczole") manufactured by Line Chemie. Registered trademark) P, etc.

Examples of the amine-based hardener include hardeners having one or more amine groups in one molecule, and examples include aliphatic amines, polyetheramines, alicyclic amines, and aromatic amines. Among them, From the viewpoint of exerting the desired effect of the present invention, aromatic amines are preferred. The amine-based hardener is preferably a first-level amine or a second-level amine, and more preferably a first-level amine. Specific examples of the amine-based hardener include 4,4'-methylene bis(2,6-dimethylaniline), diphenyldiamine sulfone, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl ash, 3,3'-diaminodiphenyl ash, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine , 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diamine Biphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4 ,4-Diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3 -Bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'- Bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl) phenanthrene, bis(4-(3-aminophenoxy)phenyl) phenanthrene, etc. . Commercially available products can be used as the amine-based hardener, for example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA", "KAYAHARD AB", "KAYAHARD AS", Mitsubishi Chemical Co., Ltd. manufactured by Nippon Kayaku Co., Ltd. Company-made "EPIKURE W" etc.

Examples of the acid anhydride-based curing agent include a curing agent having one or more acid anhydride groups in one molecule. Specific examples of the anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and methyl Nadi anhydride, hydrogenated methyl nadi anhydride, trialkyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl Yl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxy Diphthalic dianhydride, 3,3'-4,4'-diphenylbenzene tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2 ,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydride trimellitate), copolymerized styrene and horse Polymeric acid anhydrides such as styrene and maleic acid resins.

Among the above, as the (B) hardener, from the viewpoint of remarkably obtaining the desired effect of the present invention, it is preferably one selected from the group consisting of phenol-based hardeners, active ester-based hardeners, and carbodiimide-based hardeners. More than one species.

(A) The ratio of the amount of fluorine-containing epoxy resin to (B) hardener, as the ratio of [total number of epoxy groups of (A) component]: [total number of reactive groups of (B) hardener], It is preferably in the range of 1:0.1 to 1:20, more preferably 1:0.5 to 1:10, and even more preferably 1:1 to 1:5. Here, the "(A) number of epoxy groups of fluorine-containing epoxy resin" refers to the mass of the non-volatile components of (A) fluorine-containing epoxy resin present in all resin compositions divided by epoxy The equivalent value is the total value. In addition, the "(B) active group number of the hardener" refers to a value obtained by dividing the mass of the non-volatile components of the (B) hardener present in the entire resin composition by the value of the equivalent of the active group. By setting the amount ratio of (A) fluorine-containing epoxy resin to (B) hardener in this range, the desired effect of the present invention can be obtained remarkably, and the heat resistance of the hardened material of the resin composition layer is generally further improved .

(B) The content of the hardener is preferably 1% by mass or more, and more preferably 3% by mass or more relative to 100% by mass of the nonvolatile component in the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. It is even more preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

<(C) Styrene-based elastomer> The resin composition contains (C) a styrene-based elastomer. (C) The styrene-based elastomer is generally highly compatible with (A) a fluorine-containing epoxy resin, (B) a curing agent, and (D) a resin having a radical polymerizable unsaturated group. Therefore, the phase separation of (A) component and (B) component and (D) component can be suppressed. According to this, a cured product having excellent viscosity stability of the resin varnish and high adhesion strength with the copper foil after the HAST test can be obtained.

As the (C) styrene-based elastomer, any elastomer including a repeating unit (styrene unit) having a structure obtained by polymerizing styrene can be used. (C) The styrene-based elastomer may be a copolymer that is combined with styrene units and includes any repeating units different from the aforementioned styrene units.

Examples of the arbitrary repeating unit include a repeating unit having a structure obtained by polymerizing conjugated diene (conjugated diene unit), a repeating unit having a structure obtained by hydrogenating the same (hydrogenated conjugated diene unit), and the like.

Examples of conjugated dienes include aliphatic conjugates such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene. Diene; halogenated aliphatic conjugated diene such as chloroprene. As the conjugated diene, from the viewpoint of remarkably obtaining the effects of the present invention, an aliphatic conjugated diene is preferred, and butadiene is more preferred. The conjugated diene may be used alone or in combination of two or more.

(C) Although the styrene-based elastomer may be a random copolymer, from the viewpoint of remarkably obtaining the effects of the present invention, a block copolymer is preferred. The (C) styrene-based elastomer is preferably a styrene-conjugated diene block copolymer or a hydrogenated styrene-conjugated diene copolymer. Particularly preferred as (C) styrene-based elastomers include, for example, at least one end block having a polymer block containing styrene units, and at least one middle block containing: a conjugated diene unit or a hydrogenated copolymer Block copolymers of polymerized blocks of conjugated diene units.

The so-called hydrogenated styrene-conjugated diene block copolymer means a block copolymer having a structure obtained by unsaturated bonds of the hydrogenated styrene-conjugated diene block copolymer. Generally, this hydrogenated styrene-conjugated diene block copolymer is a hydrogenated aliphatic unsaturated bond, and an aromatic unsaturated bond such as a benzene ring is not hydrogenated.

Specific examples of the (C) styrene-based elastomer include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-butadiene diblock copolymer, hydrogenated styrene-butadiene block copolymer, hydrogen addition Styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer, etc.

(C) The weight average molecular weight (Mw) of the styrene-based elastomer is preferably from 1,000 to 500,000, more preferably from 2000 to 300,000, and even more preferably from 3000 to the viewpoint of significantly obtaining the desired effect of the present invention. 200000. (C) The weight average molecular weight of the styrene-based elastomer can be measured by the same method as the weight average molecular weight of (A) the fluorine-containing epoxy resin.

As the content of styrene units in the (C) styrene-based elastomer, when the (C) component is set to 100% by mass, it is preferably 61% by mass or more, more preferably 63% by mass or more, and even more preferably 65 Mass% or more. The upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less. By setting the content of the styrene unit within this range, the compatibility of (A) fluorine-containing epoxy resin and (B) hardener with (D) component can be improved, and as a result, the modification can further enhance the resin varnish The stability of viscosity. The content of the aforementioned styrene unit can be measured by, for example, the amount of the monomer constituting the component (C).

(C) A commercially available product can be used as a component, for example, hydrogenated styrene-based thermoplastic elastomers "H1041", "Tuftec H1043", "Tuftec P2000", "Tuftec MP10" (manufactured by Asahi Kasei Corporation); epoxidized styrene-butyl Diene thermoplastic elastomers "EPOFRIENDAT501" and "CT310" (manufactured by Daicel); modified styrene elastomers with hydroxyl groups "SEPTON HG252" (manufactured by Kuraray); modified styrene elastomers with carboxyl groups "Tuftec" "N503M", modified styrene elastomer with amine group "Tuftec N501", modified styrene elastomer with acid anhydride group "Tuftec M1913" (manufactured by Asahi Kasei Chemical Company); unmodified styrene elastomer " SEPTON S8104" (manufactured by Kuraray), etc. (C) The component may be used alone or in combination of two or more.

(C) From the viewpoint of remarkably obtaining the effect of the present invention, when the nonvolatile component in the resin composition is set to 100% by mass, it is preferably 0.5% by mass or more, and more preferably 0.6% by mass or more. More preferably, it is 0.7 mass% or more. The upper limit is preferably 18% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less and 4% by mass or less.

The content of the styrene unit is the content of the (C) styrene-based elastomer which is 61% by mass or more when the (C) component is set to 100% by mass. From the viewpoint of remarkably obtaining the effect of the present invention, the resin composition In the case where the non-volatile content is set to 100% by mass, it is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and even more preferably 0.7% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less and 4% by mass or less.

The content when the non-volatile component in the resin composition of (C) component is 100% by mass is defined as C1, and the content when the non-volatile component in the resin composition of (B) component is defined as 100% by mass is defined as B1. In this case, from the viewpoint of remarkably obtaining the effects of the present invention, C1/B1 is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and More preferably, it is 3 or less.

<(D) Resin with radical polymerizable unsaturated group> The resin composition contains (D) a resin having a radical polymerizable unsaturated group. By including (D) a resin having a radical polymerizable unsaturated group in the resin composition, it becomes a hardened product with a low dielectric tangent. When using (D) a resin having a radically polymerizable unsaturated group, in addition to the hardened material usually reducing the dielectric tangent, (D) component is separated from (A) component and (B) component, there is a reduction in resin The tendency of viscosity stability of varnish. However, in the present invention, by further containing (C) component in combination, phase separation is suppressed, and a cured product with excellent viscosity stability and low dielectric tangent can be obtained in resin varnish.

(*表示鍵結部)。The radical polymerizable unsaturated group refers to a group having an ethylenic double bond that shows hardening by irradiation with active energy rays. Examples of such groups include vinyl, vinylphenyl, acryl and methacryl, maleimide, fumaryl, and maleyl, preferably vinyl benzene. At least one of a group, acryl group and methacryl group. Here, the acryloyl group and the methacryloyl group are collectively referred to as "(meth)acryloyl group". In addition, the so-called vinyl phenyl group has a structure shown below.

(* indicates the bonding part).

(D) The resin having a radical polymerizable unsaturated group preferably has two or more radical polymerizable unsaturated groups per molecule from the viewpoint of obtaining a cured product having a low dielectric tangent.

(D) The resin having a radical polymerizable unsaturated group preferably has a ring structure from the viewpoint of obtaining a cured product with a low dielectric tangent. The ring structure is preferably a divalent ring group. The divalent cyclic group may be any of a cyclic group containing an alicyclic structure and a cyclic group containing an aromatic ring structure. In addition, the divalent cyclic group may have plural numbers.

From the standpoint of significantly obtaining the desired effect of the present invention, the bivalent cyclic group is preferably a 3-membered ring or more, more preferably a 4-membered ring or more, and still more preferably a 5-membered ring or more, preferably 20 members Below the ring, it is better to be below 15 member rings, and even better to be below 10 member rings. The bivalent cyclic group may have a single ring structure or a multi-ring structure.

In the ring of a divalent cyclic group, the skeleton of the ring can be constituted by hetero atoms other than carbon atoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, nitrogen atoms, and the like, and oxygen atoms are preferred. The hetero atom may have one or more than two in the aforementioned ring.

(2價之基(xii)、(xiii)中，R¹ 、R² 、R⁵ 、R⁶ 、R⁷ 、R¹¹ 及R¹² 分別獨立表示鹵素原子、碳原子數為6以下之烷基或苯基，R³ 、R⁴ 、R⁸ 、R⁹ 及R¹⁰ 分別獨立表示氫原子、鹵素原子、碳原子數6以下之烷基或苯基)。Specific examples of the divalent cyclic group include the following divalent groups (i) to (xiii).

(In the divalent groups (xii) and (xiii), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹¹ and R ¹² each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or Phenyl, R ³ , R ⁴ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group).

Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. A methyl group is preferred. R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ¹¹ and R ¹² preferably represent a methyl group. R ³ , R ⁴ , R ⁸ , R ⁹ and R ^{10 are} preferably hydrogen atoms or methyl groups.

(式(a)中，R²¹ 、R²² 、R²⁵ 、R²⁶ 、R²⁷ 、R³¹ 、R³² 、R³⁵ 及R³⁶ 分別獨立表示鹵素原子、碳原子數為6以下之烷基或苯基，R²³ 、R²⁴ 、R²⁸ 、R²⁹ 、R³⁰ 、R³³ 及R³⁴ 分別獨立表示氫原子、鹵素原子、碳原子數6以下之烷基或苯基。n及m表示0～300之整數。惟，排除n及m之一者為0的情況)。In addition, a divalent cyclic group can be combined with a plurality of divalent cyclic groups. As a specific example when combining divalent cyclic groups, a divalent cyclic group (divalent group (a)) represented by the following formula (a) can be cited.

(In formula (a), R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ , R ³² , R ³⁵ and R ³⁶ each independently represent a halogen atom, an alkyl group having 6 or less carbon atoms or benzene Radicals, R ²³ , R ²⁴ , R ²⁸ , R ²⁹ , R ³⁰ , R ³³ and R ³⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group or a phenyl group having 6 or less carbon atoms. n and m represent 0 to 300 Integer, except that one of n and m is 0).

R ²¹ , R ²² , R ³⁵ and R ³⁶ are the same as R ¹ in the divalent group (xii). R ²³ , R ²⁴ , R ³³ and R ³⁴ are the same as R ³ in the divalent group (xii). R ²⁵ , R ²⁶ , R ²⁷ , R ³¹ and R ³² are the same as R ⁵ in formula (xiii). R ²⁸ , R ²⁹ and R ³⁰ are the same as R ⁸ in formula (xiii).

n and m represent integers from 0 to 300. However, the case where one of n and m is 0 is excluded. As n and m, the integer of 1-100 is preferable, the integer of 1-50 is more preferable, and the integer of 1-10 is still more preferable. n and m may be the same or different.

As the divalent cyclic group, a divalent group (x), a divalent group (xi) or a divalent group (a) is preferred, and a divalent group (x) or a divalent group is more preferred (a).

The divalent cyclic group may have a substituent. Examples of such substituents include halogen atom, alkyl group, alkoxy group, aryl group, aralkyl group, silane group, acetyl group, acetyl group, carboxyl group, sulfo group, cyano group, nitro group, hydroxy group, Mercapto group, oxo group and the like are preferably alkyl groups.

The radical polymerizable unsaturated group may be directly bonded to a divalent cyclic group, or may be bonded through a divalent linking group. Examples of the divalent linking group include alkylene, alkenyl, aryl, heteroaryl, -C(=O)O-, -O-, -NHC(=O)-, and -NC( =O)N-, -NHC(=O)O-, -C(=O)-, -S-, -SO-, -NH-, etc., can be the basis for plural combinations of these. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and even more preferably an alkylene group or carbon atom having 1 to 5 carbon atoms Number 1 to 4 alkylene. The alkylene group may be any of linear, branched, and cyclic. Examples of such alkylene groups include methylene group, ethyl group, propyl group, butyl group, pentyl group, hexanyl group, 1,1-dimethylethyl group, etc. Methyl, ethylidene, 1,1-dimethylethylidene. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 6 carbon atoms, and still more preferably an alkenyl group having 2 to 5 carbon atoms. As the arylene group and heteroarylene group, a aryl group or heteroarylene group having 6 to 20 carbon atoms is preferred, and an arylene group or heteroarylene group having 6 to 10 carbon atoms is more preferred. As the divalent linking group, alkylene is preferred, and among them, methylene and 1,1-dimethylethylidene are preferred.

(式(1)中，R¹ 及R⁴ 分別獨立表示自由基聚合性不飽和基，R² 及R³ 分別獨立表示2價之連結基。環A表示2價之環狀基)。(D) The resin having a radical polymerizable unsaturated group is preferably represented by the following formula (1).

(In formula (1), R ¹ and R ⁴ each independently represent a radical polymerizable unsaturated group, and R ² and R ³ each independently represent a divalent linking group. Ring A represents a divalent cyclic group).

R ¹ and R ⁴ each independently represent a radical polymerizable unsaturated group, preferably vinylphenyl and (meth)acryloyl.

R ² and R ³ each independently represent a divalent linking group. The divalent linking group is the same as the divalent linking group described above.

Ring A represents a divalent cyclic group. The ring A is the same as the above-mentioned divalent cyclic group.

Ring A may have a substituent. The substituent is the same as the substituent which may have the above-mentioned divalent cyclic group.

(n1係與式(a)中之n相同，m1係與式(a)中之m相同)。Although specific examples of the component (D) are shown below, the present invention is not limited to this.

(n1 is the same as n in formula (a), and m1 is the same as m in formula (a)).

(D) As a component, commercially available products can be used, for example, "OPE-2St" manufactured by Mitsubishi Gas Chemical Co., "A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., and "DCP-A" manufactured by Kyoeisha Chemical Co., Ltd. Wait. (D) One component may be used alone, or two or more components may be used in combination.

(D) The number average molecular weight of the component is preferably 3000 or less, more preferably 2500 or less, and even more preferably 2000 or less and 1500 or less from the viewpoint of remarkably obtaining the desired effect of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, and still more preferably 500 or more and 1,000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

(D) The content of the component is from the viewpoint of remarkably obtaining the effect of the present invention. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more. It is more preferably 15% by mass or more. The upper limit is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

<(E) Inorganic filler> In addition to the above-mentioned components, the resin composition may further contain (E) an inorganic filler as an optional component.

As the material of the inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , Titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate. Among these, it is particularly suitable for silicon dioxide. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, and the like. In addition, as the silica, spherical silica is preferred. (E) The inorganic filler may be used alone or in combination of two or more.

(E) Commercial products of inorganic fillers include, for example, "UFP-30" manufactured by Electrochemical Corporation; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Materials Corporation; manufactured by Admatechs. "YC100C", "YA050C", "YA050C-MJE", "YA010C"; "SYLFIL NSS-3N", "SYLFIL NSS-4N", "SYLFIL NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ" manufactured by Admatechs Corporation ", "SO-C4", "SO-C2", "SO-C1"; etc.

(E) The average particle diameter of the inorganic filler is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm from the viewpoint of remarkably obtaining the desired effect of the present invention. Below, it is more preferably 2 μm or less, and still more preferably 1 μm or less.

(E) The average particle size of the inorganic filler can be measured by laser diffraction/scattering method according to Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering particle size distribution measuring device, and the median diameter can be determined as the average particle size. The measured sample can be used to weigh 100 mg of inorganic filler and 10 g of methyl ethyl ketone in a medicine bottle and disperse it in ultrasound for 10 minutes. The measurement sample can use a laser diffraction particle size distribution measuring device, the wavelength of the light source is set to blue and red, and the volume-based particle size distribution of (E) the inorganic filler is measured by the flow cell method. The diameter distribution calculates the average particle diameter as the median diameter. As a laser diffraction type particle size distribution measuring apparatus, for example, "LA-960" manufactured by HORIBA, Ltd. can be cited.

(E) a specific surface area of the inorganic filler, according to the present invention give significant from the viewpoint of the desired effect, is preferably 1m ² / g or more, more preferably 2m ² / g or more, particularly preferably 3m ² / g or more . Although the upper limit is not particularly limited, it is preferably 60 m ² /g or less, 50 m ² /g or less, or 40 m ² /g or less. The specific surface area was obtained by using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, adsorbing nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

(E) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organic silazane compounds. , Titanate coupling agent, etc. In addition, the surface treatment agent may be used alone or in combination of two or more kinds.

Examples of commercially available products for surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethyl) manufactured by Shin-Etsu Chemical Co., Ltd. Oxysilane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (Long-chain epoxy type silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably within a specified range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100 parts by mass of the inorganic filler is preferably 0.2 to 5 parts by mass of the surface treatment agent, more preferably 0.2 to 3 parts by mass, and even more preferably 0.3 parts by mass. ~ 2 parts by mass of surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and even more preferably 0.2 mg/ from the viewpoint of improving the dispersibility of the inorganic filler. m ² or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin varnish and the melt viscosity in the form of a sheet, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and even more preferably 0.5 mg /m ² or less.

The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (such as methyl ethyl ketone (MEK)). Specifically, as a solvent, a sufficient amount of MEK is added to an inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

(E) The content of the inorganic filler from the viewpoint of reducing the dielectric tangent, when the nonvolatile content in the resin composition is set to 100% by mass, preferably 50% by mass or more, more preferably 51% by mass or more, Even more preferably, it is 52% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

＜(F) Hardening accelerator＞ The resin composition may further contain (F) a hardening accelerator as an optional component in addition to the above-mentioned components.

Examples of the hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, and a metal-based hardening accelerator. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferable, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferable. One type of hardening accelerator may be used alone, or two or more types may be used in combination.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium Decanoate.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-reference (Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8- Diazabicyclic ring (5,4,0)-undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl trimellitic acid imidazolium, 1-cyanoethyl-2-benzene Imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamine-6 -[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate Acid adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2 -The imidazole compound such as phenylimidazoline and the adduct of the imidazole compound and the epoxy resin are preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

As the imidazole-based hardening accelerator, a commercially available product can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Examples of the guanidine hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethyl guanidine. Guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl- 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl Biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., Preferred are dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as acetone cobalt (II) and acetone cobalt (III), and organic copper complexes such as acetone copper (II). Organic zinc complexes such as acetylacetonate zinc (II), organic iron complexes such as acetoacetone iron (III), organic nickel complexes such as acetoacetone nickel (II), acetoacetone manganese ( II) Organic manganese complexes, etc. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

(F) The content of the hardening accelerator from the viewpoint of remarkably obtaining the desired effect of the present invention, when the nonvolatile component in the resin composition is set to 100% by mass, preferably 0.01% by mass or more, more preferably 0.03 The mass% or more, still more preferably 0.05 mass% or more, preferably 0.3 mass% or less, more preferably 0.2 mass% or less, and even more preferably 0.1 mass% or less.

<(G) polymerization initiator> The resin composition may further contain (G) a polymerization initiator as an optional component in addition to the above-mentioned components. (G) The polymerization initiator has a function of promoting the crosslinking of the radically polymerizable unsaturated group usually contained in the component (D). (G) The polymerization initiator may be used alone, or two or more kinds may be used in combination.

Examples of the (G) polymerization initiator include t-butyl cumene peroxide, t-butyl peroxyacetate, and α,α′-bis(t-butylperoxy)diisopropyl Benzene, t-butyl peroxylaurate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate, etc. peroxide.

Examples of commercially available products as (G) polymerization initiators include "PERBUTYL C", "PERBUTYL A", "PERBUTYL P", "PERBUTYL L", "PERBUTYL O", and "PERBUTYL ND" manufactured by NOF Corporation. , "PERBUTYL Z", "PERCUMYL P", "PERCUMYL D", etc.

(G) The content of the polymerization initiator From the viewpoint of remarkably obtaining the desired effect of the present invention, when the nonvolatile component in the resin composition is set to 100% by mass, it is preferably 0.01% by mass or more, and more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.3 mass% or less.

＜(H) epoxy resin＞ The resin composition may further contain (H) an epoxy resin as an optional component in addition to the above-mentioned components. However, (A) fluorine-containing epoxy resin is not included in (H) epoxy resin.

Examples of the (H) epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and dicyclopentadiene type. Epoxy resin, phenolic epoxy resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol Epoxy resin, onion epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic ring Oxygen resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin Resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. (H) The epoxy resin may be used alone or in combination of two or more.

When the resin composition has (H) epoxy resin, the resin composition is preferably (H) epoxy resin, and it is preferably an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of remarkably obtaining the desired effect of the present invention, the proportion of epoxy resin having two or more epoxy groups in one molecule is preferably 100% by mass of the non-volatile component of (H) epoxy resin. It is 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

(H) Among epoxy resins, there are epoxy resins which are liquid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) and epoxy resins which are solid at a temperature of 20°C (hereinafter sometimes referred to as “liquid epoxy resins”) It is called "solid epoxy resin"). As the (H) epoxy resin, the resin composition may include only liquid epoxy resin, solid epoxy resin, or a combination of liquid epoxy resin and solid epoxy resin.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. Resin.

The solid epoxy resin is preferably a biscresol-type epoxy resin, a naphthalene-type epoxy resin, a naphthalene-type 4-functional epoxy resin, a cresol novolac-type epoxy resin, and a dicyclopentadiene-type epoxy resin. Resin, phenolic epoxy resin, naphthol epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin, onion epoxy resin, bisphenol A epoxy resin, tetraphenyl ethyl Alkyl epoxy resin.

Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type 4-functional epoxy resin) manufactured by DIC. ); "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolac epoxy resin) made by DIC; "HP-7200" made by DIC ", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" manufactured by DIC Corporation , "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (Japanese phenol type epoxy resin) manufactured by Nippon Kayaku Co.; "" "NC7000L" (naphthol novolac epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl epoxy resin) manufactured by Nippon Kayaku; manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. "ESN475V" (naphthol-type epoxy resin); "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Corporation; "YX4000H", "YX4000", "YL6121" manufactured by Mitsubishi Chemical Corporation "(Biphenyl type epoxy resin); "YX4000HK" (bixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (green onion type epoxy resin) manufactured by Mitsubishi Chemical Corporation; Osaka Gas Chemical Company "PG-100" and "CG-500" manufactured by Mitsubishi Chemical Corporation; "YL7800" (fungated epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER1031S" (tetraphenylethane epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These can be used alone or in combination of two or more.

The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

The liquid epoxy resin is preferably bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, Phenolic novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, glycidyl amine epoxy resin, and butadiene Constructed epoxy resin.

Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC; "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation. ", "EPIKOTE 828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolak) manufactured by Mitsubishi Chemical Corporation Type epoxy resin); "630" and "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (bisphenol A type epoxy resin and double (Phenol F-type epoxy resin mixed product); "EX-721" (glycidyl ester epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel Resin); "PB-3600" (epoxy resin with butadiene structure) manufactured by Daicel; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl ring) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Hexane epoxy resin), etc. These can be used alone or in combination of two or more.

As the (H) epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used in combination, the equivalent ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:1 in mass. 1:20, more preferably 1:1.5 to 1:15, and particularly preferably 1:2 to 1:10. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, the desired effect of the present invention can be obtained remarkably.

(H) The epoxy equivalent and weight average molecular weight of the epoxy resin are the same as (A) the fluorine-containing epoxy resin.

(H) The content of the epoxy resin is 100% by mass, preferably 1% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability , More preferably 2% by mass or more, and even more preferably 3% by mass or more. From the viewpoint of remarkably obtaining the desired effect of the present invention, the upper limit of the content of the epoxy resin is preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

＜(I)Other additives＞ In addition to the above-mentioned components, the resin composition may further contain other additives as optional components. Examples of such additives include thermoplastic resins (however, (C) and (D) components are excluded); organic fillers; resins such as tackifiers, defoamers, leveling agents, and adhesion-imparting agents. Additives; etc. These additives can be used alone or in combination of two or more.

<Physical properties and uses of resin composition> A resin varnish in which a resin composition is dissolved in an organic solvent shows excellent viscosity stability. For example, even if the resin varnish is stored at 23°C for 1 hour, there is usually sufficient fluidity of the resin varnish, and the resin varnish can be used to make a resin sheet.

The cured product of the resin composition heat-cured at 200°C for 90 minutes shows a characteristic of low dielectric tangent. Therefore, the aforementioned hardened material brings an insulating layer with a low dielectric tangent. The dielectric tangent is preferably 0.005 or less, more preferably 0.0045 or less, and 0.004 or less. On the other hand, although the lower limit value of the dielectric tangent is not particularly limited, it may be 0.0001 or more. The aforementioned evaluation of the dielectric tangent can be measured according to the method described in the examples described later.

The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes showed excellent adhesion (copper foil peel strength) to the copper foil before the usual HAST test. Therefore, the copper foil peel strength with the copper foil before the HAST test is preferably 0.5 kgf/cm or more, more preferably 0.6 kgf/cm or more, and even more preferably 0.7 kgf/cm or more. On the other hand, although the upper limit of the adhesion strength before the HAST test is not particularly limited, it may be 5 kgf/cm or less. The evaluation of the adhesion with the copper foil before the aforementioned HAST test can be measured according to the method described in the examples described later.

The cured product obtained by heat curing the resin composition at 190°C for 90 minutes showed excellent adhesion to the copper foil (copper foil peel strength) after the HAST test. Therefore, the aforementioned hardened product provides an insulating layer excellent in adhesion to the copper foil after the HAST test. The copper foil peel strength with the copper foil after the HAST test is preferably 0.3 kgf/cm or more, more preferably 0.32 kgf/cm or more, and still more preferably 0.33 kgf/cm or more. On the other hand, although the upper limit of the adhesion strength after the HAST test is not particularly limited, it may be 5 kgf/cm or less. The evaluation of the adhesion with the copper foil after the aforementioned HAST test can be measured according to the method described in the examples described later.

The cured product is heat-cured at 130°C for 30 minutes and then at 170°C for 30 minutes. The cured product exhibits excellent adhesion strength (peel strength) with a generally plated conductor layer. Therefore, the aforementioned hardened product brings an insulating layer excellent in peel strength from the plated conductor layer. The peel strength is preferably 0.3 kgf/cm or more, more preferably 0.4 kgf/cm or more, and still more preferably 0.5 kgf/cm or more. On the other hand, although the upper limit of the peel strength is not particularly limited, it may be 5 kgf/cm or less. The aforementioned evaluation of the peel strength can be measured according to the method described in the examples described later.

The resin composition of the present invention can reduce the dielectric tangent, and can bring an insulating layer that usually has a large peel strength. Accordingly, the resin composition of the present invention can be suitably used as a resin composition for insulation purposes. Specifically, it can be suitably used as a resin composition for forming the insulating layer for forming the conductor layer (including the redistribution layer) formed on the insulating layer (resin composition for forming the insulating layer for forming the conductor layer) use.

Furthermore, the multilayer printed wiring board described later can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for forming an insulating layer of a multilayer printed wiring board), and for forming an interlayer of a printed wiring board The resin composition of the insulating layer (the resin composition for forming the interlayer insulating layer of the printed wiring board) is used. Among them, it is particularly suitable for use as a resin composition for forming an insulating layer having a through hole having a top diameter of 45 μm or less, and is particularly suitable for use as a resin composition for forming an insulating layer having a thickness of 20 μm or less.

In addition, for example, the resin composition of the present invention can also be suitably used as a resin for a redistribution layer for forming an insulating layer of a redistribution layer when manufacturing a semiconductor chip package through the following steps (1) to (6) The composition (resin composition for forming a redistribution layer) and the resin composition for sealing a semiconductor wafer (resin composition for sealing a semiconductor wafer) are used. When manufacturing a semiconductor chip package, a redistribution layer may be further formed on the sealing layer. (1) The step of temporarily fixing the film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporarily fixed film, (3) The step of forming the sealing layer on the semiconductor wafer, (4) The step of peeling the substrate and the temporary fixing film from the semiconductor wafer, (5) The step of forming a rewiring forming layer as an insulating layer on the surface where the base material of the semiconductor wafer and the temporary fixing film are peeled off and (6) Step of forming a redistribution layer as a conductor layer on the redistribution layer

In addition, since the resin composition of the present invention also provides a good insulating layer for embedding parts, it can also be suitably used in a case where a printed wiring board is a built-in circuit board.

[Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

The thickness of the resin composition layer is preferably 30 μm or less from the viewpoint that the printed wiring board is thinned and the cured product of the resin composition can provide a cured product with excellent insulation even if it is a thin film. 20 μm or less, and more preferably 15 μm or less and 10 μm or less. Although the lower limit of the thickness of the resin composition layer is not particularly limited, it can generally be 1 μm or more, 5 μm or more, or the like.

Examples of the support include films, metal foils, and release papers made of plastic materials, preferably films and metal foils made of plastic materials.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate (hereinafter referred to as Acrylic group such as polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefin, triethyl amide group, etc. Cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a foil composed of a single metal of copper, or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The support can be matted, corona-treated, or anti-static treated on the surface bonded to the resin composition layer.

In addition, as the support, a support with a release layer having a release layer on the surface for bonding to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include, for example, those selected from the group consisting of alkyd resins, polyolefin resins, urethane resins and polysiloxane resins More than one release agent. A commercially available product can be used for the support with a mold release layer. For example, a PET film with a mold release layer containing an alkyd resin-based mold release agent as a main component, "SK-1", "AL -5", "AL-7", "LumirrorT60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipiel" manufactured by Unitika, etc.

Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using the support body with a mold release layer, it is preferable that the thickness of the whole support body with a mold release layer is the said range.

In one embodiment, the resin sheet may further include other layers if necessary. Examples of this other layer include a surface provided on a support that is not joined to the support of the resin composition layer (that is, a surface opposite to the support), a protective film based on the support, and the like. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress adhesion or scratches on the surface of the resin composition layer such as dirt.

The resin sheet can be produced by, for example, preparing a resin varnish prepared by dissolving a resin composition in an organic solvent, applying the resin varnish to a support using a die coater or the like, and then drying to form a resin composition layer.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and Acetates such as carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethyl ethyl Acetamide-based solvents such as amidec (DMAc) and N-methylpyrrolidone. Organic solvents may be used alone or in combination of two or more.

Drying can be performed by well-known methods, such as heating and hot air blowing. Although the drying conditions are not particularly limited, drying is performed so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of organic solvent, the resin can be formed by drying at 50°C to 150°C for 3 to 10 minutes Composition layer.

The resin sheet can be rolled and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[Printed wiring board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

The printed wiring board can be manufactured, for example, by using the above-mentioned resin sheet and including the following steps (I) and (II). (I) The step of laminating the inner layer substrate by bonding the resin composition layer of the resin sheet on the inner layer substrate (II) The step of forming an insulating layer of the thermosetting resin composition layer

The "inner substrate" used in step (I) is a member that becomes a substrate of a printed wiring board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermal Hardened polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one side or both sides, and the conductor layer may be patterned. An inner-layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an "inner-layer circuit substrate." In addition, when manufacturing a printed wiring board, an intermediate product that should further form an insulating layer and/or a conductor layer is also included in the so-called "inner substrate" of the present invention. When the printed wiring board is a circuit board with built-in parts, the inner substrate of the built-in parts can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heating and pressing the resin sheet from the support side to the inner layer substrate. Examples of the member that heat-pressure-bonds the resin sheet to the inner layer substrate (hereinafter, also referred to as "heat-pressure-bonding member") include, for example, a heated metal plate (SUS mirror plate, etc.), a metal roll (SUS roll), and the like. In addition, it is preferable that the heating and pressure-bonding member is not directly stamped on the resin sheet, but the surface irregularities of the inner substrate are stamped through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows.

The lamination of the inner substrate and the resin sheet can be performed by a vacuum lamination method. In the vacuum lamination method, the heating and pressure bonding temperature is preferably 60°C to 160°C, more preferably 80°C to 140°C, and the heating pressure bonding pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47 In the range of MPa, the heat and pressure bonding time is preferably 20 seconds to 400 seconds, and more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under a reduced pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum press laminator manufactured by Meiji Manufacturing Co., Ltd., a vacuum applicator made by Nikko Material Co., Ltd., a batch vacuum press laminator, and the like can be cited.

After lamination, under normal pressure (at atmospheric pressure), for example, by pressing the heated pressure-bonding member from the support side, the laminated resin sheet can be smoothed. The pressing conditions for the smoothing treatment can be set to the same conditions as the above-mentioned lamination heat and pressure bonding conditions. The smoothing treatment can be performed by a commercially available laminator. Still, the lamination and smoothing treatment can be carried out continuously using the above-mentioned commercially available vacuum laminator.

The support can be removed between step (I) and step (II) or after step (II).

In step (II), the thermosetting resin composition layer forms an insulating layer. The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally used when forming the insulating layer of the printed wiring board can be used.

For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc., but the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and even more preferably 170°C ~210℃. The hardening time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preliminarily heated at a temperature lower than the curing temperature. For example, before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or more but less than 120°C (preferably 60°C or more and 115°C or less, more preferably 70°C or more and 110°C or less). More than minutes (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

Since the insulating layer is formed by the cured product of the resin composition of the present invention, the thickness of the insulating layer can be reduced. The thickness of the insulating layer is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less and 10 μm or less. Although the lower limit is not particularly limited, it can generally be 1 μm or more, 5 μm or more, or the like.

When manufacturing a printed wiring board, (III) a step of drilling an insulating layer, (IV) a step of roughening an insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be implemented in accordance with various methods well known to those of ordinary skill in the field of the invention used in the manufacture of printed wiring boards. Still, when the support is removed after step (II), the support can be removed between step (II) and step (III), between step (III) and step (IV), or step (IV) And step (V). Furthermore, if necessary, the formation of the insulating layer and the conductor layer from step (II) to step (V) can be repeated to form a multilayer wiring board.

Step (III) is a step of drilling holes in the insulating layer, whereby holes such as through holes, through holes, etc. can be formed in the insulating layer. Step (III) can be carried out using a drilling machine, laser, plasma, etc. according to the composition of the resin composition used to form the insulating layer. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board.

Since the insulating layer is formed by the cured product of the resin composition of the present invention, the top diameter can be reduced. The top diameter of the aforementioned hole is preferably 45 μm or less, more preferably 40 μm or less, and even more preferably 35 μm or less. The lower limit may be 1 μm or more.

Step (IV) is a step of roughening the insulating layer. Usually in this step (IV), the removal of gum residue is also carried out. The order and conditions of the roughening treatment are not particularly limited, and a well-known order and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. In addition, either dry type or wet type can be used. When the formation of the conductor layer is performed by sputtering, for example, it is preferably performed in a dry process such as a slag removal process using plasma. In particular, the above resin composition, when using UV (ultraviolet) laser in the drilling of step (III), has a tendency to effectively suppress the slag, so it is suitable for dry slag removal.

Examples of the gas used for sputtering include argon, oxygen, and CF ₄ . These can be used alone or in combination of two or more.

In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after roughening is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. Further, the root-mean-square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. Although the lower limit is not particularly limited, it is preferably 0.5 nm or more, more preferably 1 nm or more. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Step (V) is a step of forming a conductor layer, forming a conductor layer on the insulating layer. The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium Above the metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel, chromium alloy, copper, nickel alloy, and copper, titanium alloy) ) The formed layer. Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred The alloy layer of nickel, chromium alloy, copper, nickel alloy, copper, and titanium alloy is more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or a single metal layer of copper or an alloy of nickel and chromium alloy. Floor.

The conductor layer may have a single-layer structure, or a multi-layer structure in which two or more single metal layers or alloy layers composed of different kinds of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer bonded to the insulating layer is preferably a single metal layer of chromium, zinc or titanium or an alloy layer of nickel and chromium alloy.

Although the thickness of the conductor layer varies depending on the design of the desired printed wiring board, it is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. In the sputtering method, first, a conductor seed layer is formed on the surface of the insulating layer by sputtering, and then a conductor sputtering layer is formed on the conductor seed layer by sputtering. Before the formation of the conductor seed layer by sputtering, the surface of the insulating layer can be cleaned by reverse sputtering. As the gas used for the reverse sputtering, various gases can be used, but among them, Ar, O ₂ , and N _{2 are} preferred. When the seed layer is preferably Cu and Cu alloy, Ar or O ₂ or Ar, O ₂ mixed gas, the seed layer is Ti, Ar or N ₂ or Ar, N ₂ mixed gas, the seed layer is In the case of Cr and Cr alloys (nickel-chromium, etc.), Ar or O ₂ or a mixed gas of Ar and O ₂ . Sputtering can be performed using various sputtering devices such as a magnetron sputter, a mirror target sputter (mirrortron sputter), and the like. Examples of the metal forming the conductor seed layer include Cr, Ni, Ti, and nickel-chromium. Particularly preferred are Cr and Ti. The thickness of the conductor seed layer is usually formed so as to be preferably 5 nm or more, more preferably 10 nm or more, preferably 1000 nm or less, and more preferably 500 nm or less. Examples of the metal that forms the conductor sputtering layer include Cu, Pt, Au, and Pd. Particularly preferred is Cu. The thickness of the conductor sputtering layer is usually formed so as to be preferably 50 nm or more, more preferably 100 nm or more, preferably 3000 nm or less, and more preferably 1000 nm or less.

When the conductor seed layer is formed, the surface roughness (Ra value) formed on the surface of the insulating layer, after the conductor seed layer is removed by etching, the measured value is preferably 150 nm or less, more preferably 10 to 150 nm The range is even more preferably 10 to 120 nm or less.

After the conductor layer is formed by the sputtering method, a copper plating layer can be further formed on the conductor layer by electrolytic copper plating. The thickness of the copper plating layer is usually formed so as to be preferably 5 μm or more, more preferably 8 μm or more, preferably 75 μm or less, and more preferably 35 μm or less. For circuit formation, well-known methods such as a subtractive method and a semi-additive method can be used.

In another embodiment, the conductor layer may be formed using metal foil. When the metal foil is used to form the conductor layer, step (V) is suitable for implementation between step (I) and step (II). For example, after step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil can be carried out by a vacuum lamination method. The lamination conditions may be the same as the lamination conditions of the inner layer substrate and the resin sheet. Next, step (II) is performed to form an insulating layer. Then, by subtractive method, modified semi-additive method, etc., a conductor layer having a desired wiring pattern can be formed.

The metal foil can be produced by a well-known method such as an electrolytic method or a rolling method. Examples of the metal foil include copper foil and aluminum foil. Preferably, copper foil is used. As the copper foil, a foil composed of a single metal of copper, or a foil composed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. Examples of commercially available products of metal foil include HLP foil manufactured by JX Metals Corporation, JXUT-III foil, 3EC-III foil manufactured by Mitsui Metals Mining Corporation, and TP-III foil.

In another embodiment, the conductor layer can be formed by plating. For example, it can be plated on the surface of the insulating layer by a well-known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. From the viewpoint of ease of manufacturing, it is preferable It is formed by the semi-additive method. Hereinafter, an example in which the conductor layer is formed by the semi-additive method is shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern exposing a part of the plating seed layer is formed corresponding to the desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, the mask pattern is removed. Then, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Semiconductor device] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions) and vehicles (such as motorcycles, automobiles, trams, ships, and aircraft).

The semiconductor device of the present invention can be manufactured by mounting parts (semiconductor wafers) due to the connection of the printed wiring board. The so-called "conduction point" is "the place where the electrical signal is transmitted on the printed wiring board". The place can be the surface or the place where it is embedded. In addition, the semiconductor wafer is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The method of mounting a semiconductor wafer when manufacturing a semiconductor device is not particularly limited as long as the semiconductor wafer functions efficiently, but specifically, a wire bonding mounting method, a flip chip mounting method, The mounting method of the buildup layer (BBUL), the mounting method by the anisotropic conductive film (ACF), the mounting method by the non-conductive film (NCF), etc. Here, the so-called "mounting method by BBUL" means "mounting method of directly embedding the semiconductor wafer into the concave portion of the printed wiring board and connecting the semiconductor wafer and the wiring on the printed wiring board". [Example]

Hereinafter, the present invention will be specifically described with reference to the examples. However, the present invention is not limited to the following embodiments. In the following explanations, "parts" and "%" indicating quantities refer to "parts by mass" and "mass %", respectively, unless expressly stated otherwise. In addition, the operations described below are carried out in an environment of normal temperature and pressure unless explicitly stated otherwise.

[Measurement of peel strength (adhesion strength) of insulating layer and conductor layer] <Fabrication of Evaluation Board A> (1) Base treatment of inner layer circuit board On both sides of the glass cloth substrate epoxy resin copper-clad laminate on both sides (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation) forming the inner layer circuit, a micro-etchant ("CZ8101" manufactured by Mec Corporation) was used. ") Etching 1 μm, without roughening the copper surface.

(2) Lamination of resin sheets The resin sheets produced in the examples and comparative examples were laminated using a batch-type vacuum press laminator ("MVLP-500" manufactured by Meiji Co., Ltd.) in such a way that the resin composition layer was bonded to the inner circuit board On both sides of the inner circuit board. The lamination was performed by depressurizing for 30 seconds to reduce the gas pressure to 13 hPa or less, and performing lamination treatment at 100°C and a pressure of 0.74 MPa for 30 seconds.

(3) Hardening of the resin composition layer After laminating the resin sheet, it was heated at 100°C for 30 minutes, and then heated at 170°C for 30 minutes to thermally harden the resin composition layer to form an insulating layer.

(4) Through the formation of UV-YAG laser through holes The support was peeled off to expose the surface of the insulating layer, and a through hole was formed in the insulating layer under the following conditions using a UV-YAG laser processing machine ("LU-2L212/M50L" manufactured by Via Mechanics). Conditions: power 0.30W, number of shots 25, target top diameter 30μm

(5) After the formation of through-holes in the dry slag removal process, the inner circuit board on which the insulating layer is formed is vacuum plasma etched (100-E PLASMA SYSTEM manufactured by Tepla Corporation) in O ₂ /CF ₄ (mixed gas ratio )=25/75, vacuum condition 100Pa for 5 minutes.

(6) Formation of conductor layer by dry method Using a sputtering apparatus ("E-400S" manufactured by Canon Anelva), a titanium layer (thickness 30 nm) and a copper layer (thickness 300 nm) were formed on the insulating layer. After the obtained substrate was heated at 150°C for 30 minutes for annealing treatment, an etching resist was formed according to the semi-additive method, and after pattern formation by exposure and development, copper sulfate electrolytic plating was performed to form a thickness of 25 μm Conductor layer. After the conductor pattern is formed, it is heated at 200°C for 60 minutes to perform annealing treatment. The obtained printed wiring board is called "evaluation board A".

<Measurement of peel strength> The measurement of the peel strength of the insulating layer and the conductor layer was performed on the evaluation substrate A in accordance with JIS C6481. Specifically, a slice of a portion with a width of 10 mm and a length of 100 mm was placed in the conductor layer of the evaluation substrate A, and this end was peeled off and held with a gripper. At room temperature, it was measured that the peeling was 35 mm in the vertical direction at a speed of 50 mm/min. The load at the time (kgf/cm) was used to determine the peel strength. For the measurement system, a tensile tester ("AC-50C-SL" manufactured by TSE) was used.

[Measurement of copper foil peel strength] <Production of samples> (1) Base treatment of copper foil Immerse the glossy surface of "3EC-III" (copper foil, 35μm) manufactured by Mitsui Metals and Mines Corporation in a micro-etching agent ("CZ8101" manufactured by Mec Corporation), roughen the copper surface (Ra value = 1μm), and implement Anti-rust treatment (CL8300). This copper foil is called CZ copper foil. Furthermore, it heat-processed in the oven of 130 degreeC for 30 minutes.

(2) Lamination of copper foil and formation of insulating layer The resin sheets produced in the examples and comparative examples were formed by using a batch-type vacuum press laminator ("MVLP-500" manufactured by Meiji Co., Ltd.) with a resin composition layer and a glass cloth substrate ring forming an inner layer circuit. Lamination was performed on both sides of the above-mentioned laminate by joining two layers of oxygen-resin copper-clad laminates (copper foil thickness 18 μm, substrate thickness 0.4 mm, "R1515A" manufactured by Panasonic Corporation). The lamination process was performed by depressurizing for 30 seconds to reduce the air pressure to 13 hPa or less, and then performing pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. The support is peeled off from the laminated resin sheet. On this resin composition layer, the treated surface of the CZ copper foil was laminated under the same conditions as above. Then, the resin composition layer was cured at a curing condition of 190° C. for 90 minutes to form an insulating layer to prepare a sample.

<Measurement of copper foil peel strength (adhesion 1)> Cut the prepared sample into small pieces of 150×30 mm. Use a cutter on the copper foil part of the small piece, put a slice with a width of 10mm and a length of 100mm, peel off the end of the copper foil and hold it with a clamp ("AC-50C-SL" made by TSE), use Instron The universal testing machine measures the load when peeling 35 mm in the vertical direction at a speed of 50 mm/min at room temperature in accordance with JIS C6481.

<Measurement of copper foil peel strength (adhesion 2) after environmental test (HAST)> The prepared samples were subjected to an accelerated environmental test (environmental test) for 100 hours under the conditions of 130°C and 85%RH using a highly accelerated life test device (manufactured by Nanmoto Chemical Co., Ltd. "PM422"). Then, in the same manner as the measurement of adhesion 1, the end where the copper foil was peeled off was held with a clamp ("AC-50C-SL" manufactured by TSE), using an Instron universal testing machine, at room temperature, at 50 mm The speed per minute was measured according to JIS C6481 when the load was peeled off by 35 mm in the vertical direction.

[Determination of Dielectric Tangent] ＜Measurement･Preparation of samples for evaluation＞ After the resin sheets produced in the examples and comparative examples were heated at 200° C. for 90 minutes to thermally harden the resin composition layer, the support was peeled off. The obtained hardened product is referred to as "evaluated hardened product B".

<Determination of dielectric tangent> The hardened product for evaluation B was cut into test pieces having a width of 2 mm and a length of 80 mm. For this test piece, "HP8362B" manufactured by Agilent Technologies was used, and the dielectric tangent was measured by a cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Two test pieces were measured and the average value was calculated.

[Evaluation of Stability of Resin Varnish] The prepared resin varnish was stored at 23°C for 1 hour. Then, in the same manner as in each of the examples and comparative examples, the production of resin sheets was attempted, and the viscosity stability of the resin varnish was evaluated according to the following criteria. ○: The fluidity of the resin varnish is sufficient to make resin sheets ×: The viscosity of the resin varnish is high, and resin sheets cannot be produced

<Example 1> 15 parts of bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 238), styrene elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec" manufactured by Asahi Kasei Corporation) H1043", styrene content 67%) 3 parts were dissolved in 25 parts of toluene and 15 parts of MEK while stirring and heating. After cooling to room temperature, 46 parts of the radical polymerizable compound ("OPE-2St" manufactured by Mitsubishi Gas Chemical Co., Ltd., number average molecular weight 1200, non-volatile matter 65% by mass in toluene solution) were mixed with the radical polymerizable compound ( 30 parts of "NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326), 30 parts of active ester type hardener ("HPC8000-65T" manufactured by DIC, solid content 65% by mass in toluene solution), containing triazine Skeleton phenolic hardener ("LA-3018-50P" manufactured by DIC, 50% 2-methoxypropanol solution with a hydroxyl equivalent of about 151) 4 parts, carbodiimide hardener (Nisshinbo Chemical "V-03" manufactured by the company, active group equivalent of about 216, solid content 50% by mass in toluene solution) 8 parts, hardening accelerator (N,N-dimethyl-4-aminopyridine (DMAP), solid content 5 6 parts by mass of MEK solution), 1 part of polymerization initiator ("PERBUTYL C" manufactured by NOF Corporation), spherical surface-treated with phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") 250 parts of silicon dioxide (average particle size 0.5 μm, specific surface area 5.9 m ² /g, “SOC2” manufactured by Admatechs) were uniformly dispersed with a high-speed rotary mixer to produce a resin varnish.

Next, on the release surface of the polyethylene terephthalate film ("AL5" manufactured by Lintec Co., Ltd., thickness 38 μm) with release treatment, the thickness of the resin composition layer after drying became 20 μm The resin varnish was uniformly coated and dried at 80 to 120°C (average 100°C) for 3 minutes to produce a resin sheet.

<Example 2> 15 parts of bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight approximately 238), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec" manufactured by Asahi Kasei Corporation) P2000'', styrene content 67%) 20 parts, styrene elastomer (epoxidized styrene-butadiene thermoplastic elastomer "EPOFRIENDAT501" manufactured by Daicel, styrene content 40%) 20 parts in toluene 50 parts, MEK20 Heat while stirring to dissolve. It contains 90 parts of a radical polymerizable compound ("NK Ester A-DOG" manufactured by Shin Nakamura Chemical Industry Co., Ltd., molecular weight 326), an active ester type hardener ("EXB9416-70BK" manufactured by DIC Corporation, and an active group equivalent of about 330 28 parts of a non-volatile matter 70% by mass methyl isobutyl ketone solution), a phenolic hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, 50% of the solid content of about 151 of hydroxyl equivalent 2 -Methoxypropanol solution) 4 parts, carbodiimide-based hardener ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216, solid content 50% by mass in toluene solution) 8 parts, hardening accelerator (N,N-dimethyl-4-aminopyridine (DMAP), solid content 5 mass% MEK solution) 6 parts, polymerization initiator ("PERBUTYL C" manufactured by NOF Corporation) 1 part, phenyl group Aminosilane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated spherical silica (average particle diameter 0.3 μm, specific surface area 30.7 m ² /g, "UFP-30" manufactured by Electrochemical Corporation) 200 parts, uniformly dispersed with a high-speed rotating mixer, to produce resin varnish. The resin sheet was produced in the same manner as in the example.

<Comparative Example 1> Except for Example 1, 15 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) were changed to naphthalene type epoxy resin ("HP4032D" manufactured by DIC Corporation, epoxy equivalent of about 140) 15 servings. Except for the above matters, the same procedure as in Example 1 was carried out to prepare a resin varnish and a resin sheet.

<Comparative example 2> Except for Example 1, 3 parts of a styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Tuftec H1043" manufactured by Asahi Kasei Corporation, 67% styrene content) were not used. Except for the above matters, the same procedure as in Example 1 was carried out to prepare a resin varnish and a resin sheet.

<Comparative Example 3> Except for Example 2, 15 parts of a bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight of approximately 238) was changed to a naphthalene epoxy resin ("HP4032D" manufactured by DIC Corporation, epoxy equivalent weight of approximately 140) 15 servings. Except for the above matters, the same procedure as in Example 2 was carried out to prepare a resin varnish and a resin sheet.

<Comparative Example 4> Except for Example 2, 20 parts of styrene elastomer (hydrogenated styrene thermoplastic elastomer "Tuftec P2000" manufactured by Asahi Kasei Corporation, 67% styrene content) were not used, and styrene elastomer (Daicel Corporation) was not used. Styrene oxide-butadiene thermoplastic elastomer "EPOFRIENDAT501", styrene content 40%) 20 parts. Except for the above matters, the same procedure as in Example 2 was carried out to prepare a resin varnish and a resin sheet.

In Examples 1 to 2, it was confirmed that even if the components (E) to (G) were not contained, although the degree was poor, the results were the same as in the above examples.

Claims (16)

A resin composition comprising: (A) Fluorinated epoxy resin, (B) Hardener, (C) Styrene elastomer and (D) A resin having a radical polymerizable unsaturated group. The resin composition according to claim 1, wherein when the resin component in the resin composition is set to 100% by mass, the content of the (C) component is 0.5% by mass or more and 18% by mass or less. The resin composition according to claim 1, wherein when the (C) component is defined as 100% by mass, the content of the styrene unit in the (C) component includes 61% by mass or more. The resin composition according to claim 1, wherein the component (D) contains at least one kind selected from the group consisting of vinyl phenyl, acryl and methacryl. The resin composition according to claim 1, wherein the number average molecular weight of the component (D) is 3000 or less. The resin composition according to claim 1, wherein the content of the component (B) is 1% by mass or more and 15% by mass or less when the nonvolatile component in the resin composition is set to 100% by mass. The resin composition according to claim 1, which further contains (E) an inorganic filler. The resin composition according to claim 7, wherein the content of the component (E) is 50% by mass or more when the non-volatile content in the resin composition is set to 100% by mass. The resin composition according to claim 1 is used for forming an insulating layer. The resin composition according to claim 1, which is used to form an insulating layer for forming a conductor layer. The resin composition according to claim 1 is used for forming an insulating layer for forming a conductor layer by sputtering or metal foil. The resin composition according to claim 1, which is for forming an insulating layer having a through hole having a top diameter of 45 μm or less. The resin composition according to claim 1 is for forming an insulating layer with a thickness of 20 μm or less. A resin sheet comprising a support and a resin composition layer including the resin composition according to any one of claims 1 to 13 provided on the support. A printed wiring board comprising an insulating layer formed by a cured product of the resin composition according to any one of claims 1 to 13. A semiconductor device including the printed wiring board according to claim 15.