KR20200012773A - Resin composition - Google Patents

Abstract

Provided are: a resin composition having excellent viscosity stability of resin varnish, high adhesion strength between copper foil after HAST test, and being able to obtain a cured product having a low dielectric tangent; a resin sheet containing the resin composition; a printed wiring board having an insulating layer formed by using the resin composition; and a semiconductor device. The 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 {RESIN COMPOSITION}

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

As a manufacturing technique of a printed wiring board, the manufacturing method by the build-up system which piles up an insulating layer and a conductor layer by turns on an inner circuit board is known. In recent years, the insulation layer is required to reduce the electrical signal loss at a high frequency, and an insulation layer with a low dielectric tangent is required.

As a resin composition which forms such an insulating layer, Patent Document 1, for example, discloses a thermosetting resin having a molecular weight of 800 to 1,500 having a styrene group at (A) terminal, (B) liquid epoxy resin, (C) styrene-based thermoplastic elastomer, The resin composition which contains (D) filler and (E) hardening | curing agent and (D) component is 30-70 mass parts with respect to 100 mass parts of resin compositions is described.

Japanese Laid-Open Patent Publication No. 2016-147945

MEANS TO SOLVE THE PROBLEM This inventor examined the resin composition containing the radically polymerizable compound which makes the whole resin composition low polarization, in order to obtain the insulating layer with low dielectric tangent. As a result, when a radically polymerizable compound is contained in a resin composition, compatibility with an epoxy resin is inferior, and the new subject that the adhesive strength with copper foil after an environmental test (HAST test) in a high temperature, high humidity environment falls. . In addition, when the resin varnish in which the resin composition is dissolved in the organic solvent is preserved due to the incompatibility, the viscosity changes to gel form, that is, the viscosity stability of the resin varnish is inferior, resulting in a new resin sheet. A task was also found.

The subject of this invention is resin composition which is excellent in the viscosity stability of resin varnish, the adhesive strength between copper foil after HAST test is high, and the hardened | cured material with low dielectric tangent can be obtained; A resin sheet containing the resin composition; It is providing the printed wiring board and semiconductor device provided with the insulating layer formed using the said resin composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, in addition to (D) resin which has a radically polymerizable unsaturated group, (A) fluorine-containing epoxy resin, (B) hardening | curing agent, and (C) styrene-type elastomer are combined. It discovered that the said subject could be solved by the resin composition containing and comprised, and completed this invention.

That is, this invention includes the following content.

[1] (A) fluorine-containing epoxy resin,

(B) curing agent,

(C) styrenic elastomers, and

(D) The resin composition containing resin which has a radically polymerizable unsaturated group.

[2] The resin composition according to [1], wherein the content of the component (C) is 0.5 mass% or more and 18 mass% or less when the resin component in the resin composition is 100 mass%.

[3] The resin composition according to [1] or [2], wherein the content of the styrene unit in the component (C) includes 61 mass% or more when the component (C) is 100 mass%.

[4] The resin composition according to any one of [1] to [3], in which the component (D) contains at least one member selected from vinylphenyl group, acryloyl group, and methacryloyl group.

[5] The resin composition according to any one of [1] to [4], wherein the number average molecular weight of the component (D) is 3,000 or less.

[6] The resin composition according to any one of [1] to [5], 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 100% by mass.

[7] The resin composition according to any one of [1] to [6], further comprising (E) an inorganic filler.

[8] The resin composition according to [7], wherein the content of the component (E) is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer.

[10] The resin composition according to any one of [1] to [9], which is for forming an insulation layer for forming a conductor layer.

[11] The resin composition according to any one of [1] to [10], which is for forming an insulating layer for forming a conductor layer from sputter or metal foil.

[12] The resin composition according to any one of [1] to [11], which is for forming an insulating layer having a via hole having a top diameter of 45 μm or less.

[13] The resin composition according to 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 comprising the resin composition according to any one of [1] to [13] provided on the support.

[15] A printed wiring board comprising an insulating layer formed of the cured product of the resin composition according to any one of [1] to [13].

[16] A semiconductor device comprising the printed wiring board described in [15].

According to this invention, the resin composition which is excellent in the viscosity stability of resin varnish, the adhesive strength between copper foil after HAST test is high, and low dielectric loss tangent can be obtained; A resin sheet containing the resin composition; It is providing the printed wiring board and semiconductor device provided with the insulating layer formed using the said resin composition.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment and an illustration are shown and this invention is demonstrated in detail. However, this invention is not limited to embodiment and illustration to the following, It can change and implement arbitrarily in the range which does not deviate from the Claim of this invention, and the range of the equality.

[Resin composition]

The resin composition of this invention contains (A) fluorine-containing epoxy resin, (B) hardening | curing agent, (C) styrene-type elastomer, and (D) resin which has a radically polymerizable unsaturated group. By using such a resin composition, it becomes possible to obtain the hardened | cured material excellent in the viscosity stability of resin varnish, high adhesive strength with copper foil after a HAST test, and low dielectric tangent. In addition, by using such a resin composition, adhesive strength with copper foil can be improved normally even before a HAST test, and also peeling strength with a plating conductor layer can be raised.

The resin composition may further contain arbitrary components in combination with (A)-(D) component. As arbitrary components, (E) inorganic filler, (F) hardening accelerator, (G) polymerization initiator, (H) epoxy resin, (I) other additive, etc. are mentioned, for example. Hereinafter, each component contained in a resin composition is explained in full detail.

<(A) Fluorine-containing epoxy resin>

The resin composition contains a fluorine-containing epoxy resin as (A) component. (A) By containing a fluorine-containing epoxy resin in a resin composition, it is excellent in the viscosity stability of a resin varnish, the adhesive strength between copper foil after a HAST test is high, and it becomes possible to obtain the hardened | cured material with low dielectric tangent.

(A) As a fluorine-containing epoxy resin, the epoxy resin containing 1 or more fluorine atoms per molecule can be used. The number of fluorine atoms per molecule is preferably one or more, more preferably two or more, even more preferably three or more and five or more, and the upper limit is not particularly limited but may be 10 or less. Can be.

It is preferable that a resin composition contains resin which has two or more epoxy groups in 1 molecule as (A) fluorine-containing epoxy resin. From the viewpoint of obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the nonvolatile component of the (A) fluorine-containing epoxy resin is preferably 50% by mass or more, More preferably, it is 60 mass% or more, Especially preferably, it is 70 mass% or more.

(A) The fluorine-containing epoxy resin includes a liquid fluorine-containing epoxy resin at a temperature of 20 ° C and a fluorine-containing epoxy resin that is solid at a temperature of 20 ° C. The resin composition may contain only a liquid fluorine-containing epoxy resin as the (A) fluorine-containing epoxy resin, may contain only a solid fluorine-containing epoxy resin, and a liquid fluorine-containing epoxy resin and a solid fluorine-containing. You may contain combining epoxy resin.

Moreover, it is preferable that (A) fluorine-containing epoxy resin is aromatic fluorine-containing epoxy resin from a viewpoint of obtaining the desired effect of this invention.

As a specific example of (A) fluorine-containing epoxy resin, a bisphenol AF epoxy resin, a perfluoroalkyl type epoxy resin, etc. are mentioned. Especially, a bisphenol AF epoxy resin is preferable from a viewpoint of obtaining the desired effect of this invention. These fluorine-containing epoxy resins may be used individually by 1 type, and may be used in combination of 2 or more type.

(A) A fluorine-containing epoxy resin may use a commercial item, for example, "YL7760" (bisphenol AF type epoxy resin) by Mitsubishi Chemical Corporation, etc. are mentioned.

(A) The epoxy equivalent of a fluorine-containing epoxy resin becomes like this. Preferably it is 50 g / eq. To 5,000 g / eq., More preferably 50 g / eq. To 3,000 g / eq., More preferably 80 g / eq. To 2,000 g / eq., Even more preferably 110 g / eq. To 1,000 g / eq. By setting it as such a range, the crosslinking density of the hardened | cured material of a resin composition layer becomes enough, and the insulating layer with a small surface roughness can be formed. Epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy group. This epoxy equivalent can be measured according to JISK7236.

(A) The weight average molecular weight (Mw) of the fluorine-containing epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500 from the viewpoint of remarkably obtaining the desired effect of the present invention. to be.

The weight average molecular weight of resin can be measured as a value of polystyrene conversion by the gel permeation chromatography (GPC) method.

(A) Content of fluorine-containing epoxy resin is excellent in the viscosity stability of resin varnish, the adhesive strength between copper foil after HAST test is high, and a nonvolatile component in a resin composition from a viewpoint of obtaining hardened | cured material with low dielectric tangent. When making it 100 mass%, Preferably it is 1 mass% or more, More preferably, it is 2 mass% or more, More preferably, it is 3 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, particularly preferably 5% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention. to be. In addition, in this invention, content of each component in a resin composition is a value at the time of making non-volatile component in a resin composition 100 mass% unless there is particular notice.

<(B) Curing Agent>

The resin composition contains a curing agent as the component (B). (B) A hardening | curing agent has a function which hardens a resin composition by reacting with the (A) fluorine-containing epoxy resin normally.

As the (B) hardener, for example, an active ester hardener, a phenol hardener, a naphthol hardener, a benzoxazine hardener, a cyanate ester hardener, a carbodiimide hardener, an amine hardener, an acid anhydride hardener, etc. Can be mentioned. (B) A hardening | curing agent may be used individually by 1 type, or may use two or more types together.

As an active ester type hardening | curing agent, the compound which has 1 or more active ester group in 1 molecule can be used. Especially, as an active ester type hardening | curing agent, it has two or more ester groups with high reaction activity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxy amine ester, and ester of a heterocyclic hydroxy compound. Compounds are preferred. It is preferable that the said active ester type hardening | curing agent is obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound, a hydroxy compound, and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and / or a naphthol compound is more preferable.

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.

As the phenol compound or naphthol compound, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, a phloroglucine, benzene triol, a dicyclopentadiene type diphenol compound, a phenol novolak, etc. are mentioned. Here, a "dicyclopentadiene type diphenol compound" means the diphenol compound obtained by condensing 2 molecules of phenol to 1 molecule of dicyclopentadiene.

Preferable specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylate of phenol novolac, and a phenol. The active ester type hardening | curing agent containing the benzoylidene of novolak is mentioned. Especially, the active ester type hardening | curing agent containing a naphthalene structure and the active ester type hardening | curing agent containing a dicyclopentadiene type diphenol structure are more preferable. "Dicyclopentadiene type diphenol structure" represents the bivalent structural unit which consists of phenylene dicyclopentylene phenylene.

As a commercial item of an active ester hardening | curing agent, as an active ester hardening | curing agent containing a dicyclopentadiene type diphenol structure, it is "EXB9451", "EXB9460", "EXB9460S", "HPC8000-65T", "HPC8000H-65TM", " EXB8000L-65TM "and" EXB8150-65T "(manufactured by DIC Corporation); "EXB9416-70BK" (made by DIC Corporation) as an active ester type hardening | curing agent containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylide of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylidene of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent which is an acetylide of phenol novolac; Examples of the active ester curing agent which is a benzomonide of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation).

As a phenol type hardening | curing agent and a naphthol type hardening | curing agent, what has a novolak structure from a viewpoint of heat resistance and water resistance is preferable. Moreover, a nitrogen-containing phenol type hardening | curing agent is preferable from a viewpoint of adhesiveness with a conductor layer, and a triazine skeleton containing phenol type hardening | curing agent is more preferable.

As a specific example of a phenol type hardening | curing agent and a naphthol type hardening | curing agent, For example, "MEH-7700", "MEH-7810", "MEH-7851" by Meiwa Kasei Co., Ltd .; Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH"; "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375" manufactured by Shinnitetsu Sumikin Kagaku Corporation; "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. made by DIC Corporation are mentioned.

As an example of a benzoxazine type hardening | curing agent, "ODA-BOZ" by JFE Chemical Co., Ltd. "HFB2006M" by Showa Kobunshi company, "P-d" by Shikoku Kasei Kogyo Co., Ltd., and "F-a" are mentioned.

As a cyanate ester type hardening | curing agent, bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1, 5- phenylene cyanate), 4,4'- methylene bis (2, 6-, for example) Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4- Cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-sia Bifunctional cyanate resins such as natephenyl) thioether and bis (4-cyanatephenyl) ether; Polyfunctional cyanate resins derived from phenol novolac, cresol novolac and the like; Prepolymer etc. which these cyanate resin was partially triazineized are mentioned. As a specific example of cyanate ester type hardening | curing agent, "PT30" and "PT60" (phenol phenol novolak-type polyfunctional cyanate ester resin) by Lonza Japan company, "ULL-950S" (polyfunctional cyanate ester resin), "BA230 And "BA230S75" (a prepolymer in which part or all of the bisphenol A dicyanate is triazineated to form a trimer).

As a specific example of a carbodiimide-type hardening | curing agent, "V-03", "V-05", "V-07", "V-09" by Nisshinbo Chemical Co., Ltd .; And the like. Starbacsol (trademark) P manufactured by Rhein-Khem Co., Ltd. may be mentioned.

As an amine-type hardening | curing agent, the hardening | curing agent which has 1 or more amino group in 1 molecule is mentioned, For example, aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. are mentioned, Especially, of this invention From the viewpoint of showing the desired effect, aromatic amines are preferred. Primary amine or secondary amine is preferable, and, as for an amine hardening | curing agent, a primary amine is more preferable. Specific examples of the amine curing agent include 4,4'-methylenebis (2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone , 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylether, 3,3'-dimethyl-4,4 ' -Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 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) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. Amine-type hardener may use a commercial item, for example, "KAYABOND C-200S", "KAYABOND C-100", "Kayahad AA", "Kayahad AB", "Kayahad AS" by the Nippon Kayaku Co., Ltd. make. And "Epicure W" manufactured by Mitsubishi Chemical Corporation.

As an acid anhydride type hardening | curing agent, the hardening | curing agent which has 1 or more acid anhydride group in 1 molecule is mentioned. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydro phthalic anhydride, hexahydro phthalic anhydride, methyltetrahydro phthalic anhydride, methylhexahydro phthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride and trialkyltetrahydro phthalic anhydride. , Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromelli anhydride Acid, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic acid dianhydride, 3,3'-4,4'-diphenylsulfontetracarboxylic 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 Anhydro trimellitate, a copolymer of styrene and maleic acid Butylene, and the like polymeric-type acid anhydrides such as maleic acid resin.

Among the above-mentioned, as (B) hardening | curing agent, it is preferable that it is 1 or more types chosen from a phenol type hardening | curing agent, an active ester type hardening | curing agent, and a carbodiimide type hardening | curing agent from a viewpoint which remarkably acquires the desired effect of this invention.

(A) The ratio of fluorine-containing epoxy resin and (B) hardening | curing agent is a ratio of [total number of epoxy groups of (A) component]: [total number of reactors of (B) hardening agent], 1: 0.1-1: The range of 20 is preferable, 1: 0.5-1: 10 are more preferable, 1: 1-1: 5 are still more preferable. Here, "the number of epoxy groups of (A) fluorine-containing epoxy resin" is the value which totaled the value which divided the mass of the non-volatile component of (A) fluorine-containing epoxy resin which exists in a resin composition by epoxy equivalent. In addition, "the number of active groups of (B) hardening | curing agent" is the value which totaled the value which divided the mass of the non volatile component of the (B) hardening | curing agent which exists in a resin composition by the active group equivalent. By setting the ratio between the (A) fluorine-containing epoxy resin and the (B) curing agent within such a range, the desired effect of the present invention can be obtained remarkably, and usually, the heat resistance of the cured product of the resin composition layer is further improved.

(B) Content of a hardening | curing agent is 1 mass% or more with respect to 100 mass% of non volatile components in a resin composition from a viewpoint of remarkably obtaining the desired effect of this invention, More preferably, it is 3 mass% or more, Preferably it is 5 mass% or more, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.

<(C) styrene elastomer>

The resin composition contains (C) styrene-based elastomer. (C) Styrene-type elastomer is high in compatibility with resin which has normally (A) fluorine-containing epoxy resin, (B) hardening | curing agent, and (D) radically polymerizable unsaturated group. Therefore, phase separation of (A) component, (B) component, and (D) component can be suppressed. Therefore, it is excellent in the viscosity stability of resin varnish, and it becomes possible to obtain the hardened | cured material with high adhesive strength between copper foil after HAST test.

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 including any repeating unit different from the styrene unit in combination with the styrene unit.

As arbitrary repeating units, the repeating unit (conjugated diene unit) which has a structure obtained by superposing | polymerizing a conjugated diene, the repeating unit (hydrogenated conjugated diene unit) which has a structure obtained by hydrogenating it, etc. are mentioned, for example.

Examples of the conjugated diene include aliphatic conjugated dienes such as butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, and 1,3-hexadiene; Halogenated aliphatic conjugated dienes, such as chloroprene, etc. are mentioned. As a conjugated diene, an aliphatic conjugated diene is preferable from a viewpoint of remarkably obtaining the effect of this invention, and butadiene is more preferable. A conjugated diene may be used individually by 1 type, and may be used in combination of 2 or more type.

(C) Although a styrene-type elastomer may be a random copolymer, it is preferable that it is a block copolymer from a viewpoint which remarkably acquires the effect of this invention. As the styrene-based elastomer (C), styrene-conjugated diene block copolymers and hydrogenated styrene-conjugated diene copolymers are preferable. Particularly preferred (C) styrene-based elastomers include, for example, at least one intermediate block having a polymerized block containing styrene units as at least one terminal and a block, and further comprising a conjugated diene unit or a hydrogenated conjugated diene unit. The block copolymer contained as a block is mentioned.

Hydrogenated styrene conjugated diene block copolymer represents the block copolymer which has a structure obtained by hydrogenating the unsaturated bond of a styrene conjugated diene block copolymer. Usually, in this hydrogenated styrene-conjugated diene block copolymer, aliphatic unsaturated bonds are hydrogenated and aromatic unsaturated bonds, such as a benzene ring, are not hydrogenated.

Specific examples of the (C) styrene-based elastomers include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), and styrene. Ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-butylene-styrene block copolymer (SBBS), styrene-butadiene diblock air Copolymer, hydrogenated styrene-butadiene block copolymer, hydrogenated styrene-isoprene block copolymer, hydrogenated styrene-butadiene random copolymer and the like.

(C) The weight average molecular weight (Mw) of the styrene-based elastomer is preferably from 1,000 to 500,000, more preferably from 2,000 to 300,000, still more preferably from 3,000 to 200,000 from the viewpoint of remarkably obtaining the desired effect of the present invention. . The weight average molecular weight of (C) styrene-type elastomer can be measured by the method similar to the weight average molecular weight of (A) fluorine-containing epoxy resin.

(C) As content of the styrene unit in a styrene-type elastomer, when (C) component is 100 mass%, Preferably it is 61 mass% or more, More preferably, it is 63 mass% or more, More preferably, 65 mass% or more to be. Preferably an upper limit is 80 mass% or less, More preferably, it is 75 mass% or less, More preferably, it is 70 mass% or less. By carrying out content of a styrene unit in such a range, compatibility with (A) fluorine-containing epoxy resin, (B) hardening | curing agent, and (D) component can be heightened more, As a result, improving the viscosity stability of resin varnish more It becomes possible. Content of the said styrene unit can be measured by the injection amount of the monomer which comprises (C) component, for example.

A commercial item may be used for (C) component, For example, hydrogenated styrene-type thermoplastic elastomer "H1041", "Toughtec H1043", "Toughtec P2,000", "Toughtec MP10" (made by Asahi Kasei) ; Epoxidized styrene-butadiene thermoplastic elastomers "epoprand AT501", "CT310" (manufactured by Daicel Corporation); Modified styrene elastomer "Septon HG252" having a hydroxyl group (manufactured by Kuraresa); Modified styrene-based elastomers having a carboxyl group "Toughtec N503M", modified styrene-based elastomers having an amino group "Toughtec N501", modified styrene-based elastomers having an acid anhydride group "Toughtec M1913" (manufactured by Asahi Kasei Chemicals Co., Ltd.); Unmodified styrene-based elastomer "Septon S8104" (made by Kuraray Co., Ltd.) etc. are mentioned. (C) A component may be used individually by 1 type and may be used in combination of 2 or more type.

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

When content of a styrene unit makes (C) component 100 mass%, content of the (C) styrene-type elastomer which is 61 mass% or more is a non-volatile component in a resin composition from a viewpoint of remarkably obtaining the effect of this invention. When it is set to 100 mass%, Preferably it is 0.5 mass% or more, More preferably, it is 0.6 mass% or more, More preferably, it is 0.7 mass% or more. Preferably an upper limit is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 8 mass% or less and 4 mass% or less.

Content when the nonvolatile component in the resin composition of (C) component is 100 mass% is set to C1, and content when the nonvolatile component in the resin composition of (B) component is 100 mass% is set to B1. In this case, from the viewpoint of remarkably obtaining the effect of the present invention, C1 / B1 is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 10 or less, and more preferably 5 or less, More preferably, it is 3 or less.

<(D) Resin having a radically polymerizable unsaturated group>

The resin composition contains (D) a resin having a radical polymerizable unsaturated group. (D) By containing resin which has a radically polymerizable unsaturated group in a resin composition, it becomes possible to obtain the hardened | cured material with low dielectric tangent. When the resin having a radically polymerizable unsaturated group (D) is used, the cured product can usually lower the dielectric tangent, while the component (D) causes phase separation with the component (A) and the component (B), resulting in a resin varnish. There exists a tendency for the viscosity stability of to fall. However, in this invention, phase separation is suppressed by further combining (C) component, and it becomes possible to obtain the hardened | cured material which is excellent in the viscosity stability of resin varnish and low dielectric tangent.

A radically polymerizable unsaturated group means group which has ethylenic double bond which shows sclerosis | hardenability by irradiation of an active energy ray. As such a group, a vinyl group, a vinylphenyl group, an acryloyl group, and a methacryloyl group, a maleimide group, a fumaroyl group, a maleoyl group are mentioned, for example, A vinylphenyl group, acryloyl group, and methacrylo group are mentioned. It is preferable that it is at least 1 sort chosen from a diary.

Here, the acryloyl group and the methacryloyl group may be referred to as "(meth) acryloyl group". In addition, a vinylphenyl group is group which has a structure shown below:

(* Represents a bond)

(D) It is preferable that resin which has a radically polymerizable unsaturated group has two or more radically polymerizable unsaturated groups per molecule from a viewpoint of obtaining the hardened | cured material with low dielectric tangent.

(D) It is preferable that resin which has a radically polymerizable unsaturated group has a cyclic structure from a viewpoint of obtaining hardened | cured material with low dielectric tangent. As a cyclic structure, a bivalent cyclic group is preferable. As a bivalent cyclic group, any of the cyclic group containing an alicyclic structure and the cyclic group containing an aromatic ring structure may be sufficient. In addition, you may have two or more divalent cyclic groups.

The bivalent cyclic group is preferably a three-membered ring or more, more preferably a four-membered ring or more, even more preferably a five-membered ring or more, and preferably a 20-membered ring, from the viewpoint of remarkably obtaining the desired effect of the present invention. Hereinafter, More preferably, it is 15 or less ring, More preferably, it is 10 or less ring. Moreover, as a bivalent cyclic group, a monocyclic structure may be sufficient and a polycyclic structure may be sufficient.

As for the ring in a bivalent cyclic group, the skeleton of a ring may be comprised by hetero atoms other than a carbon atom. As a hetero atom, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned, for example, An oxygen atom is preferable. One hetero atom may have it in the said ring, and may have two or more.

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xiii):

(In bivalent group (xii) and (xiii), R <^1> , R <^2> , R <^5> , R <^6> , R <^7> , R <^11> and R <^12> are respectively independently a halogen atom, the alkyl group of 6 or less carbon atoms, Or a phenyl group, and 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)

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned. Examples of the alkyl group having 6 or less carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and the like, and are preferably methyl groups. As R <^1> , R <^2> , R <^5> , R <^6> , R <^7> , R <^11> and R <^12> , it is preferable to represent a methyl group. It is preferable that R <^3> , R <^4> , R <^8> , R <^9> and R <^10> are a hydrogen atom or a methyl group.

In addition, the divalent cyclic group may combine a plurality of divalent cyclic groups. As a specific example in the case of combining a bivalent cyclic group, the bivalent cyclic group (bivalent group (a) represented by following formula (a) is mentioned.

[Formula a]

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 a phenyl group 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 having 6 or less carbon atoms, or a phenyl group. , And an integer from 0 to 300, 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 the formula (xiii).

n and m represent the integer of 0-300. However, one of n and m is excluded. As n and m, it is preferable to represent the integer of 1-100, It is more preferable to represent the integer of 1-50, It is further more preferable to represent the integer of 1-10. n and m may be the same and may differ.

As a bivalent cyclic group, a bivalent group (x), a bivalent group (xi), or a bivalent group (a) is preferable, and a bivalent group (x) or a bivalent group (a) is more preferable.

The divalent cyclic group may have a substituent. As such a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group And an oxo group etc. are mentioned, and an alkyl group is preferable.

The radically polymerizable unsaturated group may be directly bonded to a divalent cyclic group, or may be bonded via a divalent linking group. As a bivalent coupling group, an alkylene group, an alkenylene group, an arylene group, a hetero arylene group, -C (= O) O-, -O-, -NHC (= O)-, -NC (= O) N-, -NHC (= O) O-, -C (= O)-, -S-, -SO-, -NH-, etc. can be mentioned, The group which combined these in multiple numbers may be sufficient. As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, an alkylene group having 1 to 5 carbon atoms or an alkylene group having 1 to 4 carbon atoms is more preferable. Do. The alkylene group may be any of linear, branched or cyclic. As such an alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a 1, 1- dimethyl ethylene group, etc. are mentioned, for example, A methylene group, an ethylene group, 1, 1 -Dimethylethylene group is preferred. As the alkenylene group, an alkenylene group having 2 to 10 carbon atoms is preferable, an alkenylene group having 2 to 6 carbon atoms is more preferable, and an alkenylene group having 2 to 5 carbon atoms is more preferable. As an arylene group and a heteroarylene group, the arylene group or heteroarylene group of 6-20 carbon atoms is preferable, and the arylene group or heteroarylene group of 6-10 carbon atoms is more preferable. As a bivalent coupling group, an alkylene group is preferable and a methylene group and 1, 1- dimethylethylene group are especially preferable.

(D) It is preferable that resin which has a radically polymerizable unsaturated group is represented by following General formula (1).

[Formula 1]

(In formula 1, R <^1> and R <^4> respectively independently represents a radically polymerizable unsaturated group, and R <^2> and R <^3> respectively independently represent a bivalent coupling group. Ring A represents a bivalent cyclic group)

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

R ² and R ³ each independently represent a divalent linking group. As a bivalent coupling group, it is the same as the said bivalent coupling group.

Ring A represents a divalent cyclic group. As ring A, it is the same as said bivalent cyclic group.

Ring A may have a substituent. As a substituent, it is the same as the substituent which the said divalent cyclic group may have.

Hereinafter, although the specific example of (D) component is shown, this 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)

A commercial item may use the (D) component, for example, "OPE-2St" by Mitsubishi Gas Kagaku Co., Ltd., "A-DOG" by Shin-Nakamura Kagaku Kogyo Co., Ltd., "" by Kyoeisha Kagaku Co., Ltd. DCP-A ”etc. are mentioned. (D) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The number average molecular weight of the component (D) is preferably 3,000 or less, more preferably 2,500 or less, still more preferably 2,000 or less and 1,500 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, still more preferably 500 or more and 1,000 or more. The number average molecular weight is the number average molecular weight of polystyrene conversion measured using gel permeation chromatography (GPC).

When content of (D) component makes the nonvolatile component in a resin composition 100 mass% from a viewpoint of remarkably obtaining the effect of this invention, Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more, More preferably, it is 15 mass% or more. Preferably an upper limit is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.

<(E) inorganic filler>

The resin composition may further contain the inorganic filler (E) as an optional component in addition to the above components.

An inorganic compound is used as a material of an inorganic filler. Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, carbonate Calcium, 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, zirconium titanate, zirconate Barium acid, calcium zirconate, zirconium phosphate and zirconium tungsten phosphate. Among these, silica is particularly suitable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. Moreover, as silica, spherical silica is preferable. (E) An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

As a commercial item of the (E) inorganic filler, it is "UFP-30" by the Denka Corporation, for example; "SP60-05" and "SP507-05" manufactured by Shinnitetsu Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" by Ado-Matex Corporation; "Handwriting NSS-3N", "Handwriting NSS-4N", "Handwriting NSS-5N" by Tokuyama Co .; "SC2,500SQ", "SO-C4", "SO-C2", "SO-C1", etc. made by Ado-Matex Corporation are mentioned.

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

(E) The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, it can measure by making a particle diameter distribution of an inorganic filler on a volume basis with a laser diffraction scattering type particle diameter distribution measuring device, and making the median diameter into an average particle diameter. As a measurement sample, 100 mg of inorganic fillers and 10 g of methyl ethyl ketones were measured in a vial bottle, and what disperse | distributed for 10 minutes by ultrasonic waves can be used. Using a laser diffraction particle diameter distribution measuring device, the measurement sample was used as the light source wavelengths blue and red, and the particle size distribution based on the volume basis of the (E) inorganic filler was measured by a flow cell method. The average particle diameter can be calculated from the average diameter. As a laser diffraction type particle diameter distribution measuring apparatus, "LA-960" by Horiba Corporation | KK Corporation is mentioned, for example.

(E) The specific surface area of the inorganic filler is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, particularly preferably 3 m 2 / g or more from the viewpoint of remarkably obtaining the desired effect of the present invention. to be. Although there is no restriction | limiting in particular in an upper limit, Preferably it is 60 m <2> / g or less, 50 m <2> / g or less, or 40 m <2> / g or less. A specific surface area is obtained by adsorb | sucking nitrogen gas to a sample surface using a specific surface area measuring apparatus (Macsorb HM-1210 by Mountain Tech Co., Ltd.) according to a BET method, and calculating specific surface area using the BET multipoint method.

(E) It is preferable that an inorganic filler is processed with the surface treating agent from a viewpoint of improving moisture resistance and dispersibility. As the surface treatment agent, for example, a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane, an organosilazane compound, a titanate-based coupler Ring agent etc. are mentioned. In addition, a surface treating agent may be used individually by 1 type, and may be used combining two or more types arbitrarily.

As a commercial item of a surface treating agent, Shin-Etsu Kagaku Kogyo Co., Ltd. "KBM403" (3-glycidoxy propyltrimethoxysilane), Shin-Etsu Kagaku Kogyo Co., Ltd. "KBM803" (3-mercaptopropyl trimethoxy) Silane), Shin-Etsu Kagaku Kogyo Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Kagaku Kogyo Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Kagaku Kogyo Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Kagaku Kogyo Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Kagaku Kogyo Co., Ltd. "KBM-4803" (long chain epoxy type silane coupler) Ring agent) and "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc. are mentioned.

It is preferable that the grade of the surface treatment by a surface treating agent exists in a predetermined range from a viewpoint of the dispersibility improvement of an inorganic filler. Specifically, it is preferable that 100 parts by mass of the inorganic filler is surface-treated with a surface treating agent of 0.2 parts by mass to 5 parts by mass, preferably surface treated with 0.2 parts by mass to 3 parts by mass, and 0.3 parts by mass to 2 parts by mass. It is preferable that it is surface-treated.

The degree of surface treatment by a surface treating agent can be evaluated according to the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility 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 / m 2 or more. On the other hand, 1 mg / m <2> or less is preferable, 0.8 mg / m <2> or less is more preferable, and 0.5 mg / m <2> or less is more preferable from a viewpoint of suppressing the raise of the melt viscosity of a resin varnish and the sheet | seat viscosity.

The amount of carbon per unit surface area of the inorganic filler can be measured after washing the inorganic filler after the surface treatment with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treating agent, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After the supernatant is removed and the solids are dried, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Seisakusho Co., etc. can be used.

The content of the inorganic filler (E) is preferably 50% by mass or more, more preferably 51% by mass or more, from the viewpoint of lowering the dielectric tangent, when the nonvolatile component in the resin composition is 100% by mass. Preferably it is 52 mass% or more, Preferably it is 90 mass% or less, More preferably, it is 85 mass% or less, More preferably, it is 80 mass% or less.

<(F) Curing accelerator>

The resin composition may further contain (F) hardening accelerator as arbitrary components other than said component.

As a hardening accelerator, a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, a guanidine hardening accelerator, a metal hardening accelerator, etc. are mentioned, for example. Especially, a phosphorus hardening accelerator, an amine hardening accelerator, an imidazole hardening accelerator, and a metal hardening accelerator are preferable, and an amine hardening accelerator, an imidazole hardening accelerator, and a metal hardening accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

As a phosphorus hardening accelerator, a triphenyl phosphine, a phosphonium borate compound, tetraphenyl phosphonium tetraphenyl borate, n-butyl phosphonium tetraphenyl borate, tetrabutyl phosphonium decanoate, (4-methylphenyl) triphenyl, for example Phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyl triphenyl phosphonium thiocyanate, etc. are mentioned, A triphenyl phosphine and tetrabutyl phosphonium decanoate are preferable.

As an amine hardening accelerator, For example, trialkylamines, such as a triethylamine and a tributylamine, 4-dimethylaminopyridine, benzyl dimethylamine, 2,4,6- tris (dimethylaminomethyl) phenol, 1,8 -Diazabicyclo (5,4,0) -undecene, and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

As imidazole series hardening accelerator, 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2- dimethyl imidazole, 2-ethyl-4-methyl, for example. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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 imidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecyl Imidazolyl- (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-triazineisocyanuric acid moiety Water, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline And adducts of imidazole compounds such as imidazole compounds and epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

A commercial item may be used as an imidazole series hardening accelerator, For example, "P200-H50" by Mitsubishi Chemical Corporation etc. is mentioned.

Examples of the guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, and diphenylguanidine. , Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o-tolyl) biguanide, and the like. Preference is given to 1,5,7-triazacyclo [4.4.0] deca-5-ene.

As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic iron complexes such as an organic zinc complex, iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organometallic salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate and zinc stearate.

(F) When content of the hardening accelerator makes the nonvolatile component in a resin composition 100 mass% from the viewpoint of remarkably obtaining the desired effect of this invention, Preferably it is 0.01 mass% or more, More preferably, 0.03 mass% or more, More preferably, it is 0.05 mass% or more, Preferably it is 0.3 mass% or less, More preferably, it is 0.2 mass% or less, More preferably, it is 0.1 mass% or less.

<(G) polymerization initiator>

The resin composition may further contain the (G) polymerization initiator as an arbitrary component other than the above-mentioned component. The polymerization initiator (G) usually has a function of promoting crosslinking of the radically polymerizable unsaturated groups in the component (D). (G) A polymerization initiator may be used individually by 1 type, or may use two or more types together.

As the (G) polymerization initiator, for example, t-butyl cumyl peroxide, t-butyl peroxy acetate, α, α'-di (t-butylperoxy) diisopropylbenzene, t-butylperoxylaurate and peroxides such as t-butylperoxy-2-ethylhexanoate t-butylperoxy neodecanoate and t-butylperoxybenzoate.

As a commercial item of the (G) polymerization initiator, For example, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", and "Perbutyl" by Nichi Oil Co., Ltd. ND "," Perbutyl Z "," Percumyl P "," Percumyl D ", etc. are mentioned.

(G) When content of a polymerization initiator makes the nonvolatile component in a resin composition 100 mass% from a viewpoint which remarkably acquires the desired effect of this invention, Preferably it is 0.01 mass% or more, More preferably, 0.05 mass% or more, More preferably, it is 0.1 mass% or more, Preferably it is 1 mass% or less, More preferably, it is 0.5 mass% or less, More preferably, it is 0.3 mass% or less.

<(H) epoxy resin>

The resin composition may further contain (H) epoxy resin as an arbitrary material other than the above-mentioned component. However, (A) fluorine-containing epoxy resin is not included in (H) epoxy resin.

As the (H) epoxy resin, for example, a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, and naphthol Novolak-type epoxy resin, phenol novolak-type epoxy resin, tert- butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type Epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring containing epoxy resin, cyclohexane type epoxy resin, Cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin And tetraphenyl ethane type epoxy resin. (H) An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

When a resin composition contains the (H) epoxy resin, it is preferable that a resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as (H) epoxy resin. From the viewpoint of remarkably obtaining the desired effect of the present invention, the ratio of the epoxy resin having two or more epoxy groups in one molecule to 100% by mass of the nonvolatile component of the (H) epoxy resin is preferably 50% by mass or more, More preferably, it is 60 mass% or more, Especially preferably, it is 70 mass% or more.

(H) When epoxy resin is liquid at the temperature of 20 degreeC (hereinafter may be called "liquid epoxy resin"), and an epoxy resin which is solid at the temperature of 20 degreeC (henceforth "solid epoxy resin"). There is). As the (H) epoxy resin, the resin composition may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination.

As a solid epoxy resin, the solid epoxy resin which has three or more epoxy groups in 1 molecule is preferable, and the aromatic solid epoxy resin which has three or more epoxy groups in 1 molecule is more preferable.

As a solid epoxy resin, a bixylenol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a non- Phenyl type epoxy resins, naphthylene ether type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins and tetraphenylethane type epoxy resins are preferable.

As a specific example of a solid epoxy resin, "HP4032H" (naphthalene type epoxy resin) by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) by DIC Corporation; "N-690" (cresol novolak-type epoxy resin) by DIC Corporation; "N-695" (cresol novolak-type epoxy resin) by DIC Corporation; "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin) by DIC Corporation; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", and "HP6000" by a DIC company (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. "EPPN-502H" (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. "NC7000L" (naphthol novolak-type epoxy resin); Nippon Kayaku Co., Ltd. "NC3,000H", "NC3,000", "NC3,000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) by Shin-Nitetsu Sumikin Kagaku Corporation; "ESN485" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd. (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) by Mitsubishi Chemical Corporation; "YX4000HK" by Mitsubishi Chemical Corporation (Bixylenol type epoxy resin); "YX8800" (Anthracene type epoxy resin) by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" by Osaka Gas Chemical Co., Ltd .; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "JER1010" by the Mitsubishi Chemical Corporation (solid bisphenol A epoxy resin); "JER1031S" (tetraphenylethane type epoxy resin) by Mitsubishi Chemical Corporation, etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

As a liquid epoxy resin, the liquid epoxy resin which has two or more epoxy groups in 1 molecule is preferable.

Examples of the liquid epoxy resin include bisphenol A type epoxy resins, bisphenol F type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, phenol novolac type epoxy resins, and alicyclic rings having an ester skeleton. Epoxy resins having a formula epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidylamine type epoxy resin and a butadiene structure are preferable.

As a specific example of a liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) by a DIC company; Mitsubishi Chemical Corporation "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A type epoxy resin); "JER807" and "1750" by Mitsubishi Chemical Corporation (bisphenol F type epoxy resin); "JER152" (Methanol novolak-type epoxy resin) by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine type epoxy resin) by Mitsubishi Chemical Corporation; "ZX1059" by Shin-Nitetsu Sumikin Kagaku Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) by Nagase Chemtex Co., Ltd .; "Celoxide 2021P" by Daicel Corporation (alicyclic epoxy resin which has ester frame | skeleton); "PB-3600" by the Daicel company (epoxy resin which has butadiene structure); "ZX1658" and "ZX1658GS" (Liquid 1,4-glycidylcyclohexane type epoxy resin) by Shin-Nitetsu Sumikin Kagaku Co., etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

(H) When using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, these ratios (liquid epoxy resin: solid epoxy resin) are mass ratio, Preferably it is 1: 1-1: 20, More preferably, Preferably 1: 1.5 to 1:15, particularly preferably 1: 2 to 1:10. When the ratio between the liquid epoxy resin and the solid epoxy resin is in this range, the desired effect of the present invention can be remarkably obtained.

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

(H) When content of an epoxy resin makes 100 mass% of non volatile components in a resin composition from a viewpoint of obtaining the insulating layer which shows favorable mechanical strength and insulation reliability, Preferably it is 1 mass% or more, More preferably, 2 mass% or more, More preferably, it is 3 mass% or more. The upper limit of the content of the epoxy resin is preferably 15% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less from the viewpoint of remarkably obtaining the desired effect of the present invention.

<(I) other additives>

The resin composition may further contain other additives as an optional component in addition to the above components. As such an additive, For example, a thermoplastic resin (except component (C) and component (D)); Organic fillers; Resin additives, such as a thickener, an antifoamer, a leveling agent, and an adhesive imparting agent, etc. are mentioned. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.

<Physical Properties and Uses of Resin Compositions>

The resin varnish which melt | dissolved the resin composition in the organic solvent shows the characteristic which is excellent in viscosity stability. For example, even if the resin varnish is stored at 23 ° C. for 1 hour, the resin varnish is sufficiently fluidized, and it is possible to produce a resin sheet using the resin varnish.

The hardened | cured material which thermosetted the resin composition for 90 minutes at 200 degreeC shows the characteristic that dielectric loss tangent is low. Thus, the cured product forms an insulating layer having a low dielectric tangent. As dielectric loss tangent, Preferably it is 0.005 or less, More preferably, it is 0.0045 or less, 0.004 or less. The lower limit of the dielectric loss tangent is not particularly limited, but may be 0.0001 or higher. Evaluation of the said dielectric loss tangent can be measured in accordance with the method as described in the Example mentioned later.

The hardened | cured material which thermosetted the resin composition for 90 minutes at 190 degreeC shows the characteristic which is excellent in adhesiveness (copper foil peeling strength) with copper foil before a HAST test normally. Therefore, the said hardened | cured material forms the insulating layer excellent in adhesiveness with the copper foil before a HAST test. As copper foil peeling strength with copper foil before a HAST test, Preferably it is 0.5 kgf / cm or more, More preferably, it is 0.6 kgf / cm or more, More preferably, it is 0.7 kgf / cm or more. On the other hand, the upper limit of the adhesion strength before the HAST test is not particularly limited, but may be 5 kgf / cm or less. Evaluation of adhesiveness with the copper foil before the said HAST test can be measured in accordance with the method as described in the Example mentioned later.

The hardened | cured material which thermosetted the resin composition for 90 minutes at 190 degreeC shows the characteristic that adhesiveness (copper foil peeling strength) with copper foil after a HAST test is excellent. Therefore, the said hardened | cured material forms the insulating layer excellent in adhesiveness with the copper foil after a HAST test. As adhesive strength with copper foil after a HAST test, Preferably it is 0.3 kgf / cm or more, More preferably, it is 0.32 kgf / cm or more, More preferably, it is 0.33 kgf / cm or more. On the other hand, the upper limit of the adhesion strength after the HAST test is not particularly limited, but may be 5 kgf / cm or less, or the like. Evaluation of adhesiveness with the copper foil after the said HAST test can be measured in accordance with the method as described in the Example mentioned later.

The hardened | cured material which thermosetted the resin composition at 130 degreeC for 30 minutes, and then 170 degreeC for 30 minutes shows the characteristic that the adhesive strength (fill strength) between a plating conductor layer is excellent normally. Therefore, the said hardened | cured material forms the insulating layer excellent in peeling strength with a plating conductor layer. As peel strength, Preferably it is 0.3 kgf / cm or more, More preferably, it is 0.4 kgf / cm or more, More preferably, it is 0.5 kgf / cm or more. On the other hand, the upper limit of the peel strength is not particularly limited, but may be 5 kgf / cm or less, or the like. Evaluation of the said peeling strength can be measured in accordance with the method as described in the Example mentioned later.

The resin composition of this invention can make dielectric loss tangent low, and can form the insulating layer with a large peeling strength normally. Therefore, the resin composition of this invention can be used suitably as a resin composition of insulation use. Specifically, in order to form the conductor layer (including the rewiring layer) formed on the insulating layer, it can be suitably used as a resin composition for forming the insulating layer (resin composition for forming the insulating layer for forming the conductor layer). have.

Moreover, in the multilayer printed wiring board mentioned later, resin composition (resin composition for insulating layer formation of a multilayer printed wiring board) for forming the insulating layer of a multilayer printed wiring board, and resin composition (printed wiring board) for forming the interlayer insulation layer of a printed wiring board. Can be suitably used as the resin composition for forming an interlayer insulating layer. Especially, it can use especially suitably as a resin composition for insulating layer formation which has a via hole whose tower diameter is 45 micrometers or less, and can use it especially suitably as a resin composition for insulating layer formation whose thickness is 20 micrometers or less.

For example, when a semiconductor chip package is manufactured through the following (1)-(6) processes, the resin composition of this invention is a resin composition for redistribution formation layers as an insulating layer for forming a redistribution layer (cultivation). It can be used suitably also as a resin composition for linear formation layer formation, and the resin composition (resin composition for semiconductor chip sealing) for sealing a semiconductor chip. When the semiconductor chip package is manufactured, a redistribution layer may be further formed on the sealing layer.

(1) a step of laminating a temporarily fixed film on a substrate;

(2) process of temporarily fixing a semiconductor chip on a temporarily fixed film,

(3) forming a sealing layer on the semiconductor chip;

(4) a step of peeling the substrate and the temporarily fixed film from the semiconductor chip,

(5) a step of forming a redistribution forming layer as an insulating layer on the surface from which the substrate and the temporarily fixed film of the semiconductor chip are peeled off, and

(6) Process of forming redistribution layer as conductor layer on redistribution formation layer

Moreover, the resin composition of this invention can be used suitably also when a printed wiring board is a circuit board with a component from the point which forms the insulating layer with favorable component embedding.

[Resin Sheet]

The resin sheet of this invention contains a support body and the resin composition layer formed from the resin composition of this invention provided on the said support body.

The thickness of the resin composition layer is preferably 30 µm or less, more preferably 20 µm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a thin film. More preferably, they are 15 micrometers or less and 10 micrometers or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it can be 1 micrometer or more, 5 micrometers or more.

As a support body, the film, metal foil, and release paper which consist of plastics materials are mentioned, for example, The film and metal foil which consist of plastics materials are preferable.

In the case of using a film made of a plastic material as the support, as the plastic material, for example, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polyester, such as polycarbonate (hereinafter, abbreviated as "PC"), acrylic, such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. Especially, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using metal foil as a support body, copper foil, aluminum foil etc. are mentioned as metal foil, for example, copper foil is preferable. As copper foil, you may use foil which consists of a single metal of copper, and foil which consists of alloys of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good.

The support body may perform a mat process, a corona treatment, and an antistatic process on the surface joined with a resin composition layer.

In addition, as a support body, you may use the support body with a release layer which has a mold release layer in the surface joined with a resin composition layer. As a mold release agent used for the mold release layer of a support body with a mold release layer, 1 or more types of mold release agents chosen from the group which consists of an alkyd resin, a polyolefin resin, a urethane resin, and a silicone resin are mentioned, for example. A support body with a release layer may use a commercial item, for example, "SK-1", "AL-5" and "AL-" by Lintec Co., Ltd., which are PET films having a release layer containing an alkyd resin-based release agent as a main component. 7 "," Lumira T60 "by Toray Corporation," Purex "by Teijin Co.," Unipill "by Unitika, etc. are mentioned.

Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range which is 10 micrometers-60 micrometers is more preferable. In addition, when using the support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

In one embodiment, the resin sheet may further contain other layers as needed. As such other layer, the protective film etc. which conformed to the support body provided in the surface (that is, the surface on the opposite side to a support body) which are not joined to the support body of a resin composition layer, etc. are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating | stacking a protective film, adhesion | attachment and a damage | wound of dirt etc. to the surface of a resin composition layer can be suppressed.

A resin sheet can be manufactured by preparing the resin varnish which melt | dissolved the resin composition in the organic solvent, for example, apply | coating this resin varnish on a support body using a die coater etc., and drying it to form a resin composition layer. have.

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; Acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; Carbitols such as cellosolve and butyl carbitol; Aromatic hydrocarbons such as toluene and xylene; Amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

You may perform drying by well-known methods, such as heating and hot air injection. Although drying conditions are not specifically limited, It drys so that content of the organic solvent in a resin composition layer may be 10 mass% or less, Preferably it is 5 mass% or less. Although it depends also on the boiling point of the organic solvent in a resin varnish, when using the resin varnish containing the organic solvent of 30 mass%-60 mass%, for example, resin is made by drying at 50 degreeC-150 degreeC for 3 to 10 minutes. The composition layer can be formed.

A resin sheet can be wound up and preserve | saved in roll shape. When a resin sheet has a protective film, it can be used by peeling a protective film.

[Printed wiring board]

The printed wiring board of this invention contains the insulating layer formed of the hardened | cured material of the resin composition of this invention.

A printed wiring board can be manufactured by the method containing the process of following (I) and (II) using the said resin sheet, for example.

(I) The process of laminating so that the resin composition layer of a resin sheet may bond with an inner layer board | substrate on an inner layer board | substrate.

(II) Process of thermosetting a resin composition layer to form an insulating layer

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board. For example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene And ether substrates. Moreover, the said board | substrate may have a conductor layer in the single side | surface or both surfaces thereof, and this conductor layer may be pattern-processed. The inner layer substrate in which the conductor layer (circuit) is formed on one side or both sides of the substrate may be referred to as an "inner layer circuit board". In addition, when manufacturing a printed wiring board, the intermediate | middle product to which the insulating layer and / or conductor layer should further be formed is also included in the "inner layer board" said by this invention. When a printed wiring board is a circuit board with a built-in component, the inner layer board in which a component is built can be used.

Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. As a member (henceforth a "heat-compression bonding member") which heat-presses a resin sheet to an inner layer board | substrate, a heated metal plate (SUS hard plate etc.), a metal roll (SUS roll), etc. are mentioned, for example. In addition, it is preferable not to press the heat-compression member directly to the resin sheet, but to press the elastic material such as heat-resistant rubber in between so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

You may perform lamination | stacking of an inner layer board | substrate and a resin sheet by the vacuum lamination method. In the vacuum lamination method, the heat compression temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the heat compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably. Is in the range of 0.29 MPa to 1.47 MPa, and the heat crimp time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination | stacking, you may perform the smoothing process of the laminated resin sheet by pressing under pressure (at atmospheric pressure), for example, a heat-compression-bonding member from a support body side. The press conditions of the smoothing process can be made into the same conditions as the heat crimping conditions of the lamination. The smoothing process can be performed by a commercially available laminator. In addition, lamination and smoothing process may be performed continuously using the said commercial vacuum laminator.

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

In step (II), the resin composition layer is thermosetted to form an insulating layer. The thermosetting conditions of a resin composition layer are not specifically limited, You may use the conditions employ | adopted normally when forming the insulating layer of a printed wiring board.

For example, although the thermosetting conditions of a resin composition layer differ also according to the kind of resin composition etc., hardening temperature becomes like this. Preferably it is 120 degreeC-240 degreeC, More preferably, it is 150 degreeC-220 degreeC, More preferably, 170 degreeC To 210 ° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.

Before thermosetting the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or more and 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). You may preheat for 5 minutes or more (preferably 5 minutes-150 minutes, More preferably, 15 minutes-120 minutes, More preferably, 15 minutes-100 minutes).

Since an insulating layer is formed of the hardened | cured material of the resin composition of this invention, it is possible to make thickness of an insulating layer thin. As thickness of an insulating layer, Preferably it is 30 micrometers or less, More preferably, it is 20 micrometers or less, More preferably, it is 15 micrometers or less, 10 micrometers or less. Although a minimum is not specifically limited, Usually, it can be 1 micrometer or more, 5 micrometers or more.

When manufacturing a printed wiring board, you may further perform the process of perforating to an insulating layer (III), the process of roughening a (IV) insulating layer, and the process of forming a conductor layer (V). Such steps (III) to (V) may be carried out in accordance with various methods known to those skilled in the art used for the production of printed wiring boards. When the support is removed after step (II), the support is removed between step (II) and step (III), between step (III) and step (IV), or step (IV) and step (V). May be performed in between. In addition, as needed, formation of the insulating layer and conductor layer of a process (II)-a process (V) may be repeated, and a multilayer wiring board may be formed.

Step (III) is a step of puncturing the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Process (III) may be performed using a drill, a laser, a plasma, etc. according to the composition of the resin composition used for formation of an insulating layer, etc., for example. You may decide suitably the dimension and shape of a hole according to the design of a printed wiring board.

Since an insulating layer is formed of the hardened | cured material of the resin composition of this invention, it is possible to make tower diameter small. As a top diameter of the said hole, Preferably it is 45 micrometers or less, More preferably, it is 40 micrometers or less, More preferably, it is 35 micrometers or less. The minimum can be made 1 micrometer or more.

Process (IV) is a process of roughening an insulating layer. Usually, in this process (IV), smear is also removed. The procedure and conditions of the roughening process are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. Moreover, you may use dry or wet either. When forming a conductor layer with a sputter | spatter, it is preferable to carry out dry type, such as the desmear process using plasma, for example. In particular, the above resin composition tends to effectively suppress smear when a UV (ultraviolet) laser is used for perforation in step (III), and is suitable for dry desmear.

As the gas used in the sputtering, for example, there may be mentioned argon, oxygen, CF ₄ or the like. These may be used individually by 1 type and may be used in combination of 2 or more type.

In one embodiment, the arithmetic mean roughness Ra of the surface of the insulating layer after a roughening process becomes like this. Preferably it is 400 nm or less, More preferably, it is 350 nm or less, More preferably, it is 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it can be 1 nm or more. Moreover, the square root mean square roughness Rq of the surface of the insulating layer after a roughening process becomes like this. Preferably it is 400 nm or less, More preferably, it is 350 nm or less, More preferably, it is 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it can be 1 nm or more. Arithmetic mean roughness Ra and square root mean square roughness Rq of the insulating layer surface can be measured using a non-contact surface roughness meter.

Process (V) is a process of forming a conductor layer, and forms a conductor layer on an insulating layer. The conductor material used for a conductor layer is not specifically limited. In a suitable embodiment, the conductor layer comprises at least one metal selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. do. The conductor layer may be a short metal layer or an alloy layer, and as the alloy layer, for example, an alloy of two or more metals selected from the group (for example, a nickel chromium alloy, a copper nickel alloy, and a copper titanium alloy) The layer formed by) is mentioned. Among them, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper monometallic layers, nickel-chromium alloys, copper-nickel alloys, etc., from the viewpoint of the generality of the conductor layer formation, the cost, the ease of patterning, and the like. An alloy layer of a copper-titanium alloy is preferable, and a metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is more preferable.

The conductor layer may be a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different kinds of metals or alloys are laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

Although the thickness of a conductor layer is based on the design of a desired printed wiring board, it is generally 3 micrometers-35 micrometers, Preferably they are 5 micrometers-30 micrometers.

In one embodiment, the conductor layer may be formed by a sputtering method. In the sputtering method, first, a conductor seed layer is formed on the surface of an insulating layer by sputtering, and then a conductor sputtering layer is formed on the conductor seed layer by sputtering. Before forming the conductor seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. As the gas used for the reverse sputtering, may be used various kinds of gas, particularly Ar, O _2, N ₂ are preferable. Ar or O ₂ or Ar and O ₂ mixed gas when the seed layer is Cu and Cu alloy, Ar or N ₂ or Ar and N ₂ mixed gas and seed layer is Cr and Cr alloy when the seed layer is Ti If the (nichrome, etc.), the Ar or Ar and O ₂ or O ₂ gas mixture is preferred. Sputter | spatter can be performed using various sputtering apparatuses, such as a magnetron sputter and a mirror-tron sputter | spatter. Cr, Ni, Ti, nichrome, etc. are mentioned as a metal which forms a conductor seed layer. Cr and Ti are particularly preferred. The thickness of the conductor seed layer is usually 5 nm or more, more preferably 10 nm or more, preferably 1,000 nm or less, and more preferably 500 nm or less. Cu, Pt, Au, Pd etc. are mentioned as a metal which forms a conductor sputtering layer. Especially preferred is Cu. The thickness of the conductor sputter layer is usually 50 nm or more, more preferably 100 nm or more, preferably 3,000 nm or less, and more preferably 1,000 nm or less.

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

After forming a conductor layer by the sputtering method, you may further form a copper plating layer on the said conductor layer by electrolytic copper plating. The thickness of the copper plating layer is usually 5 µm or more, more preferably 8 µm or more, preferably 75 µm or less, and more preferably 35 µm or less. Well-known methods, such as a subtractive method and a semiadditive method, can be used for circuit formation.

In another embodiment, you may form a conductor layer using metal foil. When forming a conductor layer using metal foil, it is suitable to perform process (V) between process (I) and a process (II). For example, after a process (I), a support body is removed and metal foil is laminated | stacked on the surface of the exposed resin composition layer. The lamination of the resin composition layer and the metal foil may be performed by a vacuum laminating method. The conditions of lamination may be the same as the lamination conditions of the inner layer substrate and the resin sheet. Next, process (II) is performed and an insulating layer is formed. Thereafter, the conductor layer having a desired wiring pattern may be formed by a subtractive method, a modulated semi-additive method, or the like.

Metal foil can be manufactured by well-known methods, such as an electrolysis method and a rolling method, for example. As metal foil, copper foil, aluminum foil, etc. are mentioned, for example, copper foil is preferable. As copper foil, you may use foil which consists of a single metal of copper, and foil which consists of alloys of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. good. As a commercial item of metal foil, HLP foil made by JX Kinzokusha, JXUT-III foil, 3EC-III foil made by Mitsui Kinzoku Co., Ltd., TP-III foil, etc. are mentioned, for example.

In another embodiment, the conductor layer may be formed by plating. For example, by plating on the surface of an insulating layer by conventionally well-known techniques, such as a semiadditive method and a full additive method, the conductor layer which has a desired wiring pattern can be formed, and it is semi It is preferable to form by the additive method. Hereinafter, the example which forms a conductor layer by the semiadditive method is shown.

First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Subsequently, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer is formed corresponding to the desired wiring pattern. After the metal layer is formed by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, 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 this invention contains the printed wiring board of this invention. The semiconductor device of this invention can be manufactured using the printed wiring board of this invention.

Examples of the semiconductor device include various semiconductor devices provided in electrical appliances (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trams, ships, and aircrafts). Can be.

The semiconductor device of this invention can be manufactured by mounting a component (semiconductor chip) in the conduction part of a printed wiring board. A "conduction point" is a "point which transmits an electric signal in a printed wiring board", and the place may be a surface or a buried point anywhere. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting a semiconductor chip at the time of manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the method may be used in a wire bonding method, a flip chip mounting method, or a bumpless build-up layer (BBUL). The mounting method by this, the mounting method by an anisotropic conductive film (ACF), the mounting method by a nonelectroconductive film (NCF), etc. are mentioned. Here, "the mounting method by a bumpless build-up layer (BBUL)" is a "mounting method which embeds a semiconductor chip directly in the recessed part of a printed wiring board, and connects the wiring on a semiconductor chip and a printed wiring board."

EXAMPLE

EMBODIMENT OF THE INVENTION Hereinafter, an Example is shown and this invention is demonstrated concretely. However, this invention is not limited to a following example. In the following description, "part" and "%" which represent a quantity mean the "mass part" and the "mass%", respectively, unless there is particular notice. In addition, the operation demonstrated below was performed in the environment of normal temperature normal pressure, unless otherwise specified.

[Measurement of Peel Strength (adhesive strength) between the insulating layer and the conductor layer]

<Production of Evaluation Board A>

(1) Underground Treatment of Inner Layer Circuit Board

1 micrometer etching both surfaces of the glass cloth base material epoxy resin double-sided copper clad laminated board (18 micrometers of thickness of copper foil, 0.4mm of substrate thickness, Panasonic "R1515A" made of inner layer circuits) with a microetching agent ("CZ8101" by Maxa) The roughening process of the copper surface was performed.

(2) Lamination of Resin Sheets

Both sides of an inner layer circuit board were made so that the resin sheet produced by the Example and the comparative example was contacted with an inner layer circuit board so that a resin composition layer might contact an inner layer circuit board using a batch type vacuum pressurizing laminator ("MVLP-500" by Meiki Seisakusho Co., Ltd.). Stacked on. Lamination was performed by performing a lamination process for 30 second at 100 degreeC and the pressure of 0.74 Mpa after depressurizing for 30 second and making atmospheric pressure 13 hPa or less.

(3) curing of the resin composition layer

The laminated resin sheet was heated at 100 degreeC for 30 minutes, and then at 170 degreeC for 30 minutes, the resin composition layer was thermosetted, and the insulating layer was formed.

(4) Formation of Via Hole by UV-YAG Laser

The support was peeled off, the surface of the insulating layer was exposed, and via holes were formed in the insulating layer under the following conditions using a UV-YAG laser processing machine ("LU-2L212 / M50L" manufactured by Via Mechanics Co., Ltd.).

Condition: 0.30W power, 25 shots, 30 µm target tower diameter

(5) dry desmear treatment

After the formation of the via holes, the inner circuit board on which the insulating layer was formed was subjected to O ₂ / CF ₄ (mixed gas ratio) = 25/75 using a vacuum plasma etching apparatus (100-E PLASMA SYSTEM manufactured by Teppa), having a vacuum degree of 100 Pa. Under the conditions, the process was performed for 5 minutes.

(6) Formation of conductor layer by dry method

Using the sputtering apparatus ("E-400S" by Canon Anelva company), the titanium layer (thickness 30nm) and the copper layer (thickness 300nm) were formed on the insulating layer. After heating the obtained substrate for 30 minutes at 150 degreeC, and performing an annealing process, an etching resist is formed according to the semiadditive method, and after pattern formation by exposure and image development, copper sulfate electroplating is performed and it is set as the thickness of 25 micrometers. A conductor layer was formed. After conductor pattern formation, it heated for 60 minutes at 200 degreeC, and performed the annealing treatment. The obtained printed wiring board is called "evaluation board A."

<Measurement of peel strength>

The measurement of the peeling strength of an insulating layer and a conductor layer was performed based on JIS C6481 about evaluation board A. FIG. Specifically, a partial incision of width 10 mm and length 100 mm is placed in the conductor layer of the evaluation substrate A, and this end is peeled off and picked up by a picking tool, and 35 mm in the vertical direction at a rate of 50 mm / min in room temperature. The load (kgf / cm) at the time of peeling was measured and the peeling strength was calculated | required. A tensile tester ("AC-50C-SL" manufactured by TSE Corporation) was used for the measurement.

[Measurement of Copper Foil Peeling Strength]

<Production of sample>

(1) not processing of copper foil

The gloss surface of Mitsui Kinzoku Kozan Co., Ltd. "3EC-III" (electric copper foil, 35 micrometers) was immersed in the microetching agent ("CZ8101" by Maxa), and a roughening process (Ra value = 1 micrometer) is performed on the copper surface, Antirust process (CL8300) was performed. This copper foil is called CZ copper foil. Furthermore, it heat-processed for 30 minutes in 130 degreeC oven.

(2) Formation of Laminate and Insulation Layer of Copper Foil

The glass cloth base material epoxy resin double-sided copper clad laminated board (copper foil) in which the resin composition layer formed the inner layer circuit using the batch type vacuum pressurized laminator ("MVLP-500" by the Meiki company) using the resin sheet produced by the Example and the comparative example. It laminated on both surfaces of the said laminated board so that it might bond with the thickness of 18 micrometers, the thickness of a board | substrate 0.4mm, and "R1515A" by Panasonic Corporation. Lamination process was performed by pressing for 30 second at 100 degreeC and the pressure of 0.74 Mpa after depressurizing for 30 second and making atmospheric pressure 13 hPa or less. The support body was peeled from the laminated resin sheet. On the resin composition layer, the process surface of CZ copper foil was laminated on the conditions similar to the above. And the sample was produced by hardening a resin composition layer on 190 degreeC and 90 minutes of curing conditions, and forming an insulating layer.

<Measurement of Copper Foil Peeling Strength (Adhesive 1)>

The produced sample was cut into 150 x 30 mm small pieces. A small piece of copper foil is placed in a small piece of copper foil using a cutter, and a partial incision having a width of 100 mm and a length of 100 mm is placed, and one end of the copper foil is peeled off and picked up with a picking tool (`` AC-50C-SL '' manufactured by TSE Corporation), and an Instron universal testing machine. Was measured in accordance with JIS C6481 in the room temperature using 35 mm in the vertical direction at a rate of 50 mm / min.

<Measurement of Copper Foil Peeling Strength (Adhesive 2) After Environmental Test (HAST)>

The produced sample was subjected to an accelerated environmental test (environmental test) for 100 hours at 130 ° C and 85% RH using a highly accelerated life test device ("PM422" manufactured by Kusumoto Kasei Co., Ltd.). Thereafter, one end of the copper foil is peeled off and picked up with a picking tool ("AC-50C-SL" manufactured by TSE Co., Ltd.) in the same manner as the measurement of the adhesiveness 1, and a speed of 50 mm / min is used at room temperature using an Instron universal testing machine. The load at the time of removing 35 mm in the vertical direction of the furnace was measured in accordance with JIS C6481.

[Measurement of Dielectric Tangent]

<Preparation of Sample for Measurement and Evaluation>

The resin sheet produced in the Example and the comparative example was heated at 200 degreeC for 90 minutes, thermosetting the resin composition layer, and the support body was peeled off. The obtained hardened | cured material is called "hardened material B for evaluation."

Measurement of Dielectric Junction

Cured material B for evaluation was cut into the test piece of width 2mm and length 80mm. About the said test piece, the dielectric loss tangent was measured by the cavity resonance perturbation method at the measurement frequency of 5.8 GHz and the measurement temperature of 23 degreeC using "HP8362B" by Agilent Technologies. Two test pieces were measured and the average value was computed.

[Evaluation of Resin Varnish Viscosity Stability]

The produced resin varnish was stored under 23 degreeC for 1 hour. Then, similarly to each Example and the comparative example, preparation of the resin sheet was tried, and the resin varnish viscosity stability was evaluated by the following reference | standard.

○: There is sufficient fluidity of the resin varnish and a resin sheet can be produced.

X: The viscosity of the resin varnish is high and a resin sheet cannot be produced.

<Example 1>

15 parts of bisphenol AF type epoxy resin ("YL7760" made by Mitsubishi Chemical Corporation, epoxy equivalent approximately 238), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" by Asahi Kasei Co., Ltd., styrene content 67%) 3 parts, toluene It melt | dissolved by stirring, stirring 25 parts and 15 parts of MEK. After cooling to room temperature, there are 46 parts of radically polymerizable compounds ("OPE-2St" by Mitsubishi Gas Kagaku Co., Ltd., number average molecular weight 1,200, toluene solution of 65 mass% of non volatile matters), and radically polymerizable compound (Shin-Nakamura Kagaku) 30 parts of active ester type hardening | curing agent ("HPC8000-65T" made by DIC Corporation, toluene solution of 65 mass% of solid content), 30 parts of trigon skeleton containing phenolic hardening | curing agents ( `` LA-3018-50P '' manufactured by DIC Corporation, 4 parts of 2-methoxypropanol solution having a solid content of 50% of a hydroxyl equivalent of about 151, a carbodiimide-based curing agent (V-03 manufactured by Nisshinbo Chemical Co., Ltd., equivalent to an active group equivalent 8 parts of 216, toluene solution of 50 mass% of solid content, 6 parts of hardening accelerators (N, N- dimethyl- 4-aminopyridine (DMAP), MEK solution of 5 mass% of solid content), polymerization initiator ("Perbutyl product made by Nichiyu Corporation") C ") 1 part, phenylamino silane coupling agent (Shin-Etsu Chemical Co., Ltd. make," KBM57 3 '') and 250 parts of spherical silica (average particle diameter: 0.5 µm, specific surface area: 5.9 m 2 / g, manufactured by Adomatex Co., Ltd.) were mixed and uniformly dispersed with a high speed rotary mixer to produce a resin varnish. did.

Subsequently, on the release surface of the polyethylene terephthalate film (lintec company "AL5", thickness 38 micrometers) which carried out the mold release process, the resin varnish is apply | coated uniformly so that the thickness of the resin composition layer after drying may be 20 micrometers, and it is 80-120 degreeC It dried at (average 100 degreeC) for 3 minutes, and produced the resin sheet.

<Example 2>

20 parts of bisphenol AF type epoxy resin ("YL7760" by Mitsubishi Chemical Corporation, epoxy equivalent approximately 238), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Toughtec P2,000" by Asahi Kasei Co., Ltd., styrene content 67%) 20 parts 20 parts of styrene-type elastomers (the epoxidized styrene-butadiene thermoplastic elastomer "Epopren AT501" made by Daicel Corporation, styrene content 40%) were melt | dissolved, stirring 50 parts of toluene and 20 parts of MEKs. 90 parts of radically polymerizable compounds ("NK ester A-DOG" by Shin-Nakamura Kagaku Kogyo Co., Ltd., molecular weight 326), an active ester type hardening | curing agent ("EXB9416-70BK" by DIC Corporation, non-volatile matter 70 of an active group equivalent of about 330) 28 parts by mass of methyl isobutyl ketone solution) by mass, 4 parts by triazine skeleton-containing phenol-based curing agent (DIC's `` LA-3018-50P '', 2-methoxypropanol solution having a solid content of about 151, and a hydroxyl content of about 151); Carbodiimide-based curing agent (Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent approximately 216, toluene solution of 50 mass% of solid content), hardening accelerator (N, N-dimethyl-4-aminopyridine (DMAP), 6 parts of MEK solution of 5 mass% of solid content, 1 part of polymerization initiators ("Perbutyl C" by Nichiyu Corp.), and the spherical silica surface-treated with the phenylamino silane coupling agent (Shin-Etsu Kagaku Co., Ltd. make, "KBM573"). 200 parts (average particle diameter 0.3 micrometer, specific surface area 30.7 m <2> / g, "UFP-30" by Denka Co., Ltd.) were mixed. , Uniformly dispersed in a high-speed rotary mixer in the same manner as in Example 1 produce a resin varnish, and a resin sheet was produced.

Comparative Example 1

In Example 1, 15 parts of bisphenol AF type epoxy resins ("YL7760" by Mitsubishi Chemical Corporation, epoxy equivalent about 238) were changed to 15 parts of naphthalene type epoxy resins ("HP4032D" by DIC Corporation, about 140 equivalents). A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

Comparative Example 2

In Example 1, 3 parts of styrene-type elastomers (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" by Asahi Kasei Co., Ltd., styrene content 67%) were not used. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

Comparative Example 3

In Example 2, 15 parts of bisphenol AF type epoxy resins ("YL7760" by Mitsubishi Chemical Corporation, epoxy equivalent about 238) were changed to 15 parts of naphthalene type epoxy resins ("HP4032D by DIC company, about 140 equivalents"). A resin varnish and a resin sheet were produced in the same manner as in Example 2 except for the above matters.

<Comparative Example 4>

In Example 2, 20 parts of styrene-based elastomers (hydrogenated styrene-based thermoplastic elastomer "Toughtec P2,000" manufactured by Asahi Kasei Co., Ltd., styrene content 67%) are not used, and styrene-based elastomers (epoxidized styrene-butadiene manufactured by Daicel Corporation) are not used. 20 parts of thermoplastic elastomers "epofend AT501" and styrene content 40%) were not used. A resin varnish and a resin sheet were produced in the same manner as in Example 2 except for the above matters.

In Example 1 and 2, even if it does not contain (E) component-(G) component, although there was a difference in degree, it confirmed that it resulted in the same result as the said Example.

Claims (16)

(A) fluorine-containing epoxy resins,
(B) curing agent,
(C) styrenic elastomers, and
(D) The resin composition containing resin which has a radically polymerizable unsaturated group. The resin composition of Claim 1 which is 0.5 mass% or more and 18 mass% or less when content of (C) component makes the resin component in a resin composition 100 mass%. The resin composition of Claim 1 containing 61 mass% or more when content of the styrene unit in (C) component makes (C) component 100 mass%. The resin composition of Claim 1 in which (D) component contains at least 1 sort (s) chosen from a vinylphenyl group, acryloyl group, and methacryloyl group. The resin composition of Claim 1 whose number average molecular weights of (D) component are 3,000 or less. The resin composition of Claim 1 which is 1 mass% or more and 15 mass% or less when content of (B) component makes 100 mass% the nonvolatile components in a resin composition. The resin composition of Claim 1 which further contains (E) an inorganic filler. The resin composition of Claim 7 whose content of (E) component is 50 mass% or more, when the non volatile component in a resin composition is 100 mass%. The resin composition of Claim 1 which is for forming an insulation layer. The resin composition of Claim 1 which is for insulation layer formation for forming a conductor layer. The resin composition of Claim 1 which is for insulation layer formation for forming a conductor layer from sputter | spatter or metal foil. The resin composition of Claim 1 which is for forming the insulating layer which has a via hole whose tower diameter is 45 micrometers or less. The resin composition of Claim 1 which is for insulation layer formation whose thickness is 20 micrometers or less. The resin sheet containing the support body and the resin composition layer containing the resin composition of any one of Claims 1-13 provided on the said support body. The printed wiring board containing the insulating layer formed of the hardened | cured material of the resin composition of any one of Claims 1-13. The semiconductor device containing the printed wiring board of Claim 15.