KR20200012764A - Resin composition - Google Patents

Abstract

Provided are: a resin composition having excellent storage stability of resin varnish 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 contains: (A) an epoxy resin; (B) a curing agent; (C) a styrene-based elastomer; and (D) a resin having a radically polymerizable unsaturated group, wherein the content of a styrene unit in the component (C), is 61 mass% or more if the component (C) is 100 mass%.

Description

Resin composition {RESIN COMPOSITION}

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

As a manufacturing technique of a printed wiring board, the manufacturing method by the buildup system which piles up an insulation layer and a conductor layer alternately on the inner-layer circuit board and overlaps is known. In recent years, the insulation layer is required to reduce the electrical signal loss at a high frequency, and an insulation layer having 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 1500 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.

Patent Document 1: Japanese Patent Application Laid-Open 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, the new subject that the storage stability of the resin varnish which melt | dissolved the resin composition in the organic solvent is inferior was discovered.

The subject of this invention is resin composition which can obtain the hardened | cured material which is excellent in the storage stability of resin varnish, and low dielectric loss tangent; 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 resin which has a (D) radically polymerizable unsaturated group, content of (A) epoxy resin, (B) hardening | curing agent, and a styrene unit is a predetermined range ( C) It was found that the above problems can be solved by a resin composition containing a combination of styrene-based elastomers, thereby completing the present invention.

That is, this invention includes the following content.

[1] (A) epoxy resin,

(B) curing agent,

(C) styrenic elastomers, and

(D) Resin having a radical polymerizable unsaturated group

Including,

The resin composition which is 61 mass% or more when content of the styrene unit in (C) component makes 100 mass% (C) component.

[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], in which the component (D) contains at least one member selected from vinylphenyl group, acryloyl group, and methacryloyl group.

[4] The resin composition according to any one of [1] to [3], wherein the number average molecular weight of the component (D) is 3000 or less.

[5] The resin composition according to any one of [1] to [4], further comprising (E) an inorganic filler.

[6] The resin composition according to [5], 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.

[7] The resin composition according to any one of [1] to [6], which is for forming an insulating layer.

[8] The resin composition according to any one of [1] to [7], which is for forming an insulation layer for forming a conductor layer.

[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer for forming a conductor layer from sputter or metal foil.

[10] The resin composition according to any one of [1] to [9], which is for forming an insulating layer having a via hole having a top diameter of 45 μm or less.

[11] The resin composition according to any one of [1] to [10], wherein the thickness is for forming an insulating layer having a thickness of 20 µm or less.

[12] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [11] provided on the support.

[13] A printed wiring board comprising an insulating layer formed of the cured product of the resin composition according to any one of [1] to [11].

[14] A semiconductor device comprising the printed wiring board described in [13].

According to this invention, it is excellent in the storage stability of resin varnish, and the resin composition which can obtain the hardened | cured material with low dielectric tangent; Resin sheet containing the resin composition; The printed wiring board and semiconductor device provided with the insulating layer formed using the said resin composition can be provided.

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

[Resin composition]

The resin composition of this invention contains the resin which has (A) epoxy resin, (B) hardening | curing agent, (C) styrene-type elastomer, and (D) radically polymerizable unsaturated group, and content of the styrene unit in (C) component, When (C) component is 100 mass%, it is 61 mass% or more. By using such a resin composition, it becomes possible to obtain the hardened | cured material which is excellent in the storage stability of resin varnish, and low in dielectric tangent. In addition, by using such a resin composition, it is possible to raise the peeling strength with a conductor layer normally.

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

<(A) Epoxy Resin>

As the (A) 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 bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, and a tris Phenol type epoxy resin, 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 Epoxy resin, cyclohexane epoxy resin, cyclohexane dimethanol epoxy resin, naphthylene ether A foxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, etc. are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that a resin composition contains the epoxy resin which has two or more epoxy groups in 1 molecule as (A) 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 (A) epoxy resin is preferably 50% by mass or more, and more. Preferably it is 60 mass% or more, Especially preferably, it is 70 mass% or more.

The epoxy resin may be a liquid epoxy resin (hereinafter may be referred to as "liquid epoxy resin") at a temperature of 20 ° C, and an epoxy resin (hereinafter may be referred to as "solid epoxy resin") which is solid at a temperature of 20 ° C. . The resin composition may contain only the liquid epoxy resin as the epoxy resin (A), may contain only the solid epoxy resin, or may contain the liquid epoxy resin and the 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- A phenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin are preferable, and a naphthalene type epoxy resin is more 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. "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthol type epoxy resin) by Shin-Nitetsu Sumikin Chemical Co., Ltd .; "ESN485" manufactured by Shinnitetsu Sumikin Chemical 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 .; "YL7760" (Bisphenol AF type epoxy resin) by Mitsubishi Chemical Corporation; "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, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins, and phenol novolac type epoxy resins. , An alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a glycidylamine type epoxy resin, and an epoxy resin having a butadiene structure are preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin is more 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-glycidyl cyclohexane type epoxy resin) by Shin-Nitetsu Suminkagaku Co., etc. are mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

(A) 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 1: 1.5 to 1:15, and 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. Moreover, when using normally in the form of a resin sheet, moderate adhesiveness is brought. Moreover, when using normally in the form of a resin sheet, sufficient flexibility can be obtained and handleability improves. Moreover, the hardened | cured material which has sufficient breaking strength normally can be obtained.

(A) The epoxy equivalent of an epoxy resin becomes like this. Preferably it is 50g / eq.-5000g / eq., More preferably, it is 50g / eq.-3000g / eq., More preferably, it is 80g / eq. To 2000 g / eq., Even more preferably 110 g / eq. To 1000 g / eq. By setting it as this 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.

The weight average molecular weight (Mw) of the epoxy resin (A) is preferably from 100 to 5000, more preferably from 250 to 3000, still more preferably from 400 to 1500 from the viewpoint of remarkably obtaining the desired effect of the present invention.

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

(A) When content of 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. 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 reacts with the (A) epoxy resin normally and hardens a resin composition.

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 ester, thiophenol ester, N-hydroxyamine 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.

Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, and m-. Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, a fluoroglucin, 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.

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 furnace. And active ester curing agents including benzoylation of volacs. 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; As an active ester hardening | curing agent containing the acetylide of a phenol novolak, "DC808" (made by Mitsubishi Chemical Corporation); "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing a benzoylidene of phenol novolac; "DC808" (made by Mitsubishi Chemical Corporation) as an active ester hardening | curing agent which is an acetylide of a phenol novolak; 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 heat resistant and water resistant viewpoint 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 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'- methylenebis (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 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 .; Stavazol (registered trademark) P manufactured by Rheinchem 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-xylyldendiamine, 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. Can be. Amine-type hardener may use a commercial item, for example, "KAYABOND C-200S" made by Nippon Kayaku Co., Ltd. "KAYABOND C-100", "Kayahad AA", "Kayahad AB", "Kayahad AS" 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, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride and trialkyltetrahydrophthalic anhydride. , Dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride, pyromelli anhydride Acid, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic 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 Polymeric acid anhydrides, such as a styrene maleic acid resin, etc. are mentioned.

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

The ratio of (A) 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], and it is the range of 1: 0.01 to 1:20. Is preferable, 1: 0.05-1: 10 are more preferable, 1: 0.1-1: 8 are still more preferable. Here, "the number of epoxy groups of (A) epoxy resin" is the value which totaled the value which divided the mass of the non-volatile component of (A) 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) epoxy resin and the (B) curing agent within such a range, the desired effect of the present invention can be remarkably obtained, 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 0.1 mass% or more with respect to 100 mass% of non volatile components in a resin composition from a viewpoint which remarkably acquires the desired effect of this invention, More preferably, it is 0.3 mass% or more, More preferably, Preferably it is 0.5 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) styrenic elastomer. Content of the styrene unit in (C) styrene-type elastomer is 61 mass% or more, when letting (C) component be 100 mass%. Since (C) styrene-type elastomer contains 61 mass% or more of styrene units, compatibility with (A) epoxy resin, (B) hardening | curing agent, and (D) radically polymerizable unsaturated group is high. Therefore, phase separation of (A) component, (B) component, and (D) component can be suppressed. Therefore, the storage stability of resin varnish can be improved.

(C) As content of the styrene unit in a styrene-type elastomer, when (C) component is 100 mass%, it is 61 mass% or more, Preferably it is 63 mass% or more, More preferably, it is 65 mass% or more. 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) epoxy resin, (B) hardening | curing agent, and (D) component can be improved more, and as a result, the storage stability of resin varnish can be improved. Content of the said styrene unit can be measured by the injection amount of the monomer which comprises (C) component, for example.

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 this, 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 the styrene-type elastomer may be a random copolymer, it is preferable that it is a block copolymer from a viewpoint of remarkably obtaining 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) styrenic elastomers include, for example, a polymerization block containing styrene units as at least one terminal block, and at least one intermediate block containing 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, an aliphatic unsaturated bond is 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 co Polymers, hydrogenated styrene-butadiene block copolymers, hydrogenated styrene-isoprene block copolymers, hydrogenated styrene-butadiene random copolymers, and the like.

(C) The weight average molecular weight (Mw) of the styrene-based elastomer is preferably from 1000 to 500000, more preferably from 2000 to 300000, still more preferably from 3000 to 200000 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) epoxy resin.

A commercial item may be used for (C) component, For example, hydrogenated styrene-type thermoplastic elastomer "Toughtec H1043", "Toughtec P2000" (made by Asahi Kasei); Styrene-type thermoplastic elastomer "Septon 2104" (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.

Content of (C) component, when the non-volatile component in a resin composition is 100 mass% from a viewpoint of remarkably obtaining the effect of this invention, Preferably it is 0.1 mass% or more, More preferably, it is 0.3 mass% or more, Furthermore, Preferably it is 0.5 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.

Content when the nonvolatile component in the resin composition of (C) component is 100 mass% is called C1, and content when the nonvolatile component in the resin composition of (B) component is 100 mass% is called 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, more preferably 5 Hereinafter, More preferably, it is three or less.

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

The resin composition contains a resin having the (D) 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 (D) having a radically polymerizable unsaturated group 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) so that the resin varnish There exists a tendency for storage stability to fall. However, in the present invention, by further containing (C) component in combination, phase separation is suppressed, and it is possible to obtain a cured product excellent in storage stability of the resin varnish and low in 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 methacryl It is preferable that it is at least 1 sort (s) chosen from the royl group.

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

(* Indicates 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 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 ring 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 or less, more preferably from the viewpoint of remarkably obtaining the desired effect of the present invention. Is 15-membered ring or less, More preferably, it is 10-membered ring or less. 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), (xiii), R <^1> , R <^2> , R <^5> , R <^6> , R <^7> , R <^11> and R <^12> are respectively independently a halogen atom, an 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. Examples of ^{R 1, R 2, R 5} , R 6, R 7, R 11, and R ^12, preferably represents a methyl group. R ³ , R ⁴ , R ⁸ , R ⁹ , and R ¹⁰ are preferably a hydrogen atom or a methyl group.

In addition, you may combine a bivalent annular group with some bivalent annular group. 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.

(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, and 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. m represents an integer of 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 formula (xiii).

n and m represent the integer of 0-300. Except that one of n and m is 0. 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. Examples of such a substituent include 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 carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, Oxo group etc. are mentioned, 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 alkyl having 1 to 4 carbon atoms More preferably. 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- dimethylethylene 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 hetero arylene group, a C6-C20 arylene group or a hetero arylene group is preferable, and a C6-C10 arylene group or a hetero arylene group 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 formula (1).

(In formula (1), R <^1> and R <^4> represents a radically polymerizable unsaturated group each independently, and R <^2> and R <^3> respectively independently show 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 Chemical Co., Ltd., "A-DOG" by Shin-Nakamura Chemical Co., Ltd., "DCP by Kyoeisha Chemical Co., Ltd." -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 3000 or less, more preferably 2500 or less, still more preferably 2000 or less and 1500 or less from the viewpoint of remarkably obtaining the desired effect of the present invention. The lower limit is preferably 100 or more, more preferably 300 or more, still more preferably 500 or more and 1000 or more. The number average molecular weight is the number average molecular weight in terms of polystyrene measured using gel permeation chromatography (GPC).

The content of the component (D) is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of remarkably obtaining the effect of the present invention, when the nonvolatile component in the resin composition is 100% by mass. 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>

In addition to the component mentioned above, the resin composition may contain (E) inorganic filler further as arbitrary 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, titanium Barium zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungsten phosphate, and the like. Among these, silica is particularly suitable. As silica, amorphous silica, fused silica, crystalline silica, synthetic silica, aerial silica, etc. are mentioned, for example. 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 (E) inorganic filler, For example, "UFP-30" by the Denka company; "SP60-05" and "SP507-05" by Shin-Nitetsu Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" by Ado-Matex Corporation; "Handwriting NSS-3N", "Handwriting NSS-4N", "Handwriting NSS-5N" by Tokuyama Co .; "SC2500SQ", "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. It is 2 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 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 ketone were weighed out and taken in a vial bottle, and what disperse | distributed by ultrasonic wave for 10 minutes can be used. The particle size distribution obtained by making the measurement sample use the laser diffraction type particle diameter distribution measuring apparatus, and using the light source wavelength blue and red, and measuring the particle diameter distribution of the volume reference of (E) inorganic filler by the flow cell system. The average particle diameter can be calculated from the median diameter. As a laser diffraction type particle diameter distribution measuring apparatus, "LA-960" by Horiba Sesaku Sho Co., etc. 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. . 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 can be obtained by adsorb | sucking nitrogen gas to a sample surface using a specific surface area measuring device (Macsorb HM-1210 by Mountain Tech) according to a BET method, and calculating a 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, and 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 Chemical Co., Ltd. make "KBM403" (3-glycidoxy propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. make "KBM803" (3-mercaptopropyl trimethoxysilane), for example. , Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), "SZ" by Shin-Etsu Chemical Co., Ltd. -31 "(hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd." KBM103 "(phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd." KBM-4803 "(long chain epoxy type silane coupling agent), Shin-Etsu Chemical Co., Ltd. The production "KBM-7103" (3,3,3-trifluoropropyl trimethoxysilane) 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 by 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 carbon amount 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 carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" by Horiba Sesaku Sho Co., Ltd. can be used.

The content of the (E) inorganic filler 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.

<Styrene-based elastomers other than (F) (C) component>

In addition to (C) component, the resin composition may contain styrene-type elastomers other than (F) (C) component within the range which does not affect the effect of this invention. (F) Styrene-type elastomer different from (C) component means styrene-type elastomer which is less than 61 mass% when content of a styrene unit makes (F) component 100 mass%. Elements other than content of the styrene unit of (F) component may be as having demonstrated in the <(C) styrene-type elastomer> column.

As content of the styrene unit in (F) component, when (F) component is 100 mass%, it is less than 61 mass%, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less. Preferably a minimum is 1 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more. Content of the said styrene unit can be measured by the injection amount of the monomer which comprises (F) component, for example.

A commercial item may be used for (F) component, For example, Hydrogenated styrene-type thermoplastic elastomer "Toughtec MP10" (made by Asai Kasei Co., Ltd.); Epoxidized styrene-butadiene thermoplastic elastomer "Epopren AT501" (made by Daicel Corporation) etc. are mentioned. (F) A component may be used individually by 1 type and may be used in combination of 2 or more type.

The content of the component (F) is preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of remarkably obtaining the effect of the present invention, when the nonvolatile component in the resin composition is 100% by mass. Preferably it is 3 mass% or more. Preferably an upper limit is 15 mass% or less, More preferably, it is 13 mass% or less, More preferably, it is 10 mass% or less.

<(G) Curing Accelerator>

The resin composition may further contain the (G) hardening accelerator as an optional component other than the component mentioned above.

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.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 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 preferred.

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 addition , 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, etc. The adduct of an imidazole compound, an imidazole compound, and an epoxy resin is mentioned, 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 diphenyl. Guanidine, 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. Amide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferred.

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.

(G) When content of a hardening accelerator makes 100 mass% the nonvolatile components in a resin composition from a viewpoint of remarkably obtaining the desired effect of this invention, Preferably it is 0.01 mass% or more, More preferably, it is 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.

<(H) polymerization initiator>

In addition to the component mentioned above, the resin composition may further contain (H) polymerization initiator as arbitrary components. The polymerization initiator (H) usually has a function of promoting crosslinking of the radically polymerizable unsaturated group in the component (D). (H) A polymerization initiator may be used individually by 1 type, or may use two or more types together.

As the (H) 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.

(H) As a commercial item of a polymerization initiator, "Perbutyl C", "Perbutyl A", "Perbutyl P", "Perbutyl L", "Perbutyl O", "perbutyl" by Nichi Oil Corporation, for example. ND "," Perbutyl Z "," Percumyl P "," Percumyl D ", etc. are mentioned.

(H) When content of a polymerization initiator 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, 0.05 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 0.4 mass% or less.

<(I) other additives>

In addition to the component mentioned above, the resin composition may further contain other additive as an arbitrary component. As such an additive, For example, a thermoplastic resin (except component (C), component (D), and component (F)); 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 storage stability. For example, even if the resin varnish is stored at 5 ° C. for 100 hours and then returned to room temperature, aggregates of 1 mm or more are not usually observed in the resin varnish.

The hardened | cured material which thermosetted the resin composition for 90 minutes at 200 degreeC shows the characteristic of low dielectric loss tangent. Therefore, the said hardened | cured material forms the insulating layer with 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. On the other hand, the lower limit of the dielectric tangent is not particularly limited, but may be 0.0001 or more. 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 30 minutes at 130 degreeC after that for 30 minutes shows the characteristic that it is excellent in adhesive strength (fill strength) with a plating conductor layer 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. 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 for insulation use. Specifically, it can be suitably used as a resin composition (resin composition for forming an insulation layer for forming a conductor layer) for forming the insulation layer for forming a conductor layer (including a rewiring layer) formed on the insulation 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 be used 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 be used 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 ( It can be used suitably also as a resin composition for redistribution 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, an additional redistribution layer may be formed over 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) A step of forming a redistribution layer as a conductor layer on the redistribution formation layer.

Moreover, since the resin composition of this invention forms the insulation layer with favorable component embedding property, it can be used suitably also when a printed wiring board is a circuit board with a component.

[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.

When using the film which consists of a plastic material as a support body, as a plastic material, polyethylene terephthalate (it may abbreviate as "PET" hereafter), polyethylene naphthalate (henceforth abbreviated as "PEN") may be used, for example. ), Such as polyester, polycarbonate (hereinafter may be abbreviated as "PC"), polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), Polyether ketone, polyimide and the like. 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 an alloy 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., Ltd.," Unipill "by Unichika Co., 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 another 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 a protective film, adhesion and scratches of dust or the like can be suppressed on the surface of the resin composition layer.

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

As an organic solvent, For example, ketones, such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; Acetic acid 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 off 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 resin sheet mentioned above, 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. In addition, the said board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be pattern-processed. The inner layer substrate in which the conductor layer (circuit) is formed on one or both surfaces of the substrate may be referred to as an "inner layer circuit board". In addition, when manufacturing a printed wiring board, the intermediate | middle manufacture to which the insulation layer and / or conductor layer should be further 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 on 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 a heat-compression member directly to a resin sheet, but to press an elastic material, such as heat-resistant rubber, in between so that a resin sheet may fully follow the surface asperity of an inner layer board | 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 Sesaku Sho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, a smoothing treatment of the laminated resin sheets may be performed by pressing the pressurized member under normal pressure (atmospheric pressure), for example, on the support 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 commercially available 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). These processes (III) to (V) may be performed 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. Moreover, you may repeat formation of the insulating layer and conductor layer of process (II)-process (V) as needed, and may form a multilayer wiring board.

Step (III) is a step of puncturing the insulating layer, whereby holes such as via holes, through holes and the like 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 a 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, smear is also removed in this step (IV). The order and conditions of a roughening process are not specifically limited, The well-known procedure and conditions normally used when forming the insulating layer of a printed wiring board can be employ | adopted. Moreover, you may use either dry or wet. 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 resin composition described above tends to effectively suppress smear when a UV (ultraviolet) laser is used for perforation in step (III), and is suitable for dry desmear.

E. Examples of 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. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 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. The lower limit is not particularly limited, but is preferably 0.5 nm or more, more preferably 1 nm or more. Arithmetic mean roughness Ra and square root mean square roughness Rq of the surface of the insulating layer 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, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) The layer formed by) is mentioned. Among them, single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloys, copper-nickel alloys, 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 single 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.

The thickness of the conductor layer depends on the design of the desired printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by a sputtering method. In the sputtering method, first, after forming a conductor seed layer on the surface of an insulating layer by sputter | spatter, a conductor sputtering layer is formed on the said conductor seed layer by sputter | spatter. Before forming the conductor seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. As the gas used in the art reverse sputtering, may be used various kinds of gas, particularly Ar, O _2, N ₂ are preferable. Ar or O ₂ or Ar, O ₂ mixed gas when the seed layer is Cu and Cu alloy, Ar or N ₂ or Ar, N ₂ mixed gas when the seed layer is Ti, Cr and Cr alloy (Nichrome Etc.), Ar or O ₂ or Ar, O ₂ mixed gas is preferable. Sputter | spatter can be performed using various sputter apparatuses, such as a magnetron sputter and a miratron sputter | spatter. Cr, Ni, Ti, nichrome, etc. are mentioned as a metal which forms a conductor seed layer. Cr and Ti are particularly preferable. The thickness of the conductor seed layer is usually 5 nm or more, more preferably 10 nm or more, preferably 1000 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 3000 nm or less, and more preferably 1000 nm or less.

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

After forming a conductor layer by the sputtering method, you may form a copper plating layer further 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 electrolytic 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 an alloy 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 Kinzoku Co., Ltd., 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, it can plate on the surface of an insulating layer by conventionally well-known techniques, such as a semiadditive method and a full additive method, and can form the conductor layer which has a desired wiring pattern, and from a viewpoint of simplicity of manufacture, 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. Next, on the formed plating seed layer, the mask pattern which exposes a part of plating seed layer is formed corresponding to a 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, aircrafts, etc.). have.

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, but specifically, a wire bonding method, a flip chip mounting method, and a bumpless build-up layer (BBUL) The mounting method by, the mounting method by an anisotropic conductive film (ACF), the mounting method by a non-conductive film (NCF), etc. are mentioned. Here, the "mounting method by bumpless build-up (BBUL)" is a "mounting method which connects a semiconductor chip and the wiring on a printed wiring board directly by embedding a semiconductor chip in the recessed part of 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 quantity mean "mass part" and "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]

<Preparation of Sample for Measurement and Evaluation>

(1) Underground Treatment of Inner Layer Circuit Board

1 micrometer is used for both surfaces of the glass cloth base material epoxy resin double-sided copper clad laminated board (18 micrometers of copper foil, board | substrate thickness 0.4mm, Panasonic Corporation "R1515A" made of inner layer circuit) with a microetching agent ("CZ8101" by Mack Corporation) which formed the inner layer circuit. It etched and performed the roughening process of the copper surface.

(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 using a batch type vacuum pressurized laminator ("MVLP-500" manufactured by Meiki Sesakusho Co., Ltd.). Stacked on. Lamination was carried out by performing a lamination process at 100 ° C. and a pressure of 0.74 MPa for 30 seconds after reducing the pressure for 30 seconds to set the pressure to 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, and 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 to expose the surface of the insulating layer, 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 shorts, 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 Tepla), with a vacuum degree of 100 Pa. Under conditions, the treatment was performed for 5 minutes.

(6) Formation of conductor layer by dry method

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

<Measurement of peel strength>

The measurement of the peeling strength between an insulating layer and a conductor layer was performed based on JIS C6481 about evaluation board A. FIG. Specifically, a load of 10 mm in width and 100 mm in length is cut into the conductor layer of the evaluation board A, and one end is peeled off and picked up by a collector, and 35 mm is removed in the vertical direction at a rate of 50 mm / min at room temperature. (kgf / cm) 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 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 peeling off the support body. 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 this test piece, dielectric tangent was measured by the cavity resonance perturbation method at the measurement frequency of 5.8 GHz and measurement temperature of 23 degreeC using "HP8362B" by Agilent Technologies. Two test pieces were measured and the average value was computed.

[Evaluation of Preservation Stability of Resin Varnishes]

The resin varnish produced in the Example and the comparative example was stored at 5 degreeC for 100 hours. After returning to room temperature (25 degreeC), the aggregate was confirmed visually and the storage stability of the resin varnish was evaluated by the following reference | standard.

(Circle): Aggregate 1 mm or more is not observed.

X: Aggregate 1 mm or more is observed.

Example 1

15 parts of bisphenol A type epoxy resin ("828US" made by Mitsubishi Chemical Corporation, epoxy equivalent approximately 180), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" made by Asai 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, 46 parts of radically polymerizable compounds ("OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., number-average molecular weight 1200, toluene solution of 65 mass% of non volatile matters), radically polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) are here. 30 parts of teacher production "NK ester A-DOG", molecular weight 326), 28 parts of active ester type hardening | curing agents (DIC company make "EXB9416-70BK", methyl isobutyl ketone solution of 70 mass% of non volatile matters of about 330 active group equivalents), 8 parts of triazine frame | skeleton containing phenolic hardening | curing agent (DIC company "LA-3018-50P", 2-methoxypropanol solution of 50% of solid content of hydroxyl equivalent approximately 151), hardening accelerator (N, N-dimethyl-4-amino Surface of 6 parts of pyridine (DMAP), MEK solution of 5 mass% of solid content), a polymerization initiator ("Percumyl P" by Nichiyu Corporation), a phenylamino silane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573") Treated spherical silica (average particle diameter 0.5 μm, specific surface area 5.9 m 2 / g, adomatech Used to manufacture "SO-C2"), 250 parts of mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

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

Example 2

15 parts of biphenyl type epoxy resin ("NC3000L" by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 269), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Toughtec P2000" by Asai 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, 46 parts of radically polymerizable compounds ("OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., number-average molecular weight 1200, toluene solution of 65 mass% of non volatile matters), radically polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) are here. 30 parts of teacher-made "NK ester A-DOG", molecular weight 326), active ester type hardening | curing agent ("HPC8000-65T" made by DIC Corporation, toluene solution of 65 mass% of solid content), triazine skeleton containing phenolic hardening | curing agent (DIC "LA-3018-50P" made by Corporation, four parts of 2-methoxypropanol solution of 50% of solid content of hydroxyl equivalent approximately 151, carbodiimide-type hardening | curing agent ("V-03 made by Nisshinbo Chemical Company", active group equivalent approximately 216 , 8 parts of 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 C by Nichiyu Corp.) 1 part, phenylaminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. make, "KBM573") 250 parts of surface-treated spherical silica (average particle diameter: 0.5 µm, specific surface area: 5.9 m 2 / g, manufactured by Ado-Matex Co., Ltd.) were mixed and uniformly dispersed with a high speed rotary mixer to prepare a resin varnish. In the same manner as in Example 1, a resin sheet was produced.

Example 3

15 parts of biphenyl type epoxy resin ("NC3000L" by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 269), styrene-based elastomer (hydrogenated styrene-based thermoplastic elastomer "Toughtec P2000" by Asai 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, 60 parts of radically polymerizable compounds ("NK ester A-DOG" by Shin-Nakamura Kagaku Kogyo Co., Ltd., molecular weight 326), triazine skeleton containing phenolic hardener (DIC company "LA-3018-50P") , 8 parts of 2-methoxypropanol solution of 50% of solid content of hydroxyl equivalent of about 151, 6 parts of hardening accelerator (N, N-dimethyl-4-aminopyridine (DMAP), MEK solution of 5% by mass of solid content), polymerization Spherical silica (average particle diameter: 0.5 µm, specific surface area: 5.9 m2 / g) surface-treated with one part of an initiator ("Perbutyl C" manufactured by Nichiyu Co., Ltd.) and a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.). And 250 parts of &quot; SO-C2 &quot; manufactured by Ado-Matex Co., Ltd. were mixed and uniformly dispersed with a high speed rotary mixer to produce a resin varnish, and a resin sheet was produced in the same manner as in Example 1.

Example 4

15 parts of bisphenol AF type epoxy resin ("YL7760" made by Mitsubishi Chemical Corporation, epoxy equivalent approximately 238), 20 parts of styrene-type elastomers (hydrogenated styrene-type thermoplastic elastomer "Toughtec H1043" made by Asai Kasei Co., Ltd., styrene content 67%), 20 parts, 20 parts of other styrene-type elastomers (hydrogenated styrene-type thermoplastic elastomer "Toughtec MP10" made from Acai Kasei Co., Ltd., styrene content 30%) were melt | dissolved by stirring in 50 parts of toluene and 20 parts of MEK. After cooling to room temperature, 46 parts of radically polymerizable compounds ("OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., number-average molecular weight 1200, toluene solution of 65 mass% of non volatile matters), radically polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) are here. 30 parts of teacher production "NK ester A-DOG", molecular weight 326), carbodiimide system hardener ("V-03" made by Nisshinbo Chemical Co., Ltd., active group equivalent approximately 216, toluene solution of 50 mass% of solid content) 16 parts, hardening 6 parts of promoter (N, N-dimethyl-4-aminopyridine (DMAP), MEK solution of 5 mass% of solid content), a polymerization initiator ("perbutyl C" by Nichi Corporation), a phenylamino silane coupling agent (Shin-Etsu) 250 parts of spherical silica (average particle diameter: 0.5 µm, specific surface area: 5.9 m 2 / g, product made by Ado-Matex Co., Ltd.), surface-treated with Kagaku Kogyo Co., Ltd. To produce a resin varnish, and in the same manner as in Example 1 The sheet was produced.

Example 5

15 parts of bisphenol AF type epoxy resin ("YL7760" made by Mitsubishi Chemical Corporation, epoxy equivalent approximately 238), 40 parts of styrene-type elastomers (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" made by Asai Kasei Co., Ltd., styrene content 67%) 40 parts of toluene It melt | dissolved by stirring, stirring 50 parts and 20 parts of MEK. After cooling to room temperature, 46 parts of radically polymerizable compounds ("OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., number-average molecular weight 1200, toluene solution of 65 mass% of non volatile matters), radically polymerizable compound (Shin-Nakamura Chemical Co., Ltd.) are here. 30 parts of teacher production "NK ester A-DOG", molecular weight 326), 16 parts of benzoxazine type hardening | curing agents (MEK solution of 50 mass% of solid content of "ODA-BOZ" by JFE Chemical Co., Ltd.), a hardening accelerator (N, N-dimethyl 6 parts of -4-aminopyridine (DMAP), MEK solution of 5 mass% of solid content), a polymerization initiator ("perbutyl C" by Nichiyu Corp.), a phenylamino silane coupling agent (made by Shin-Etsu Chemical Co., Ltd., "KBM573" 250 parts of spherical silica (average particle diameter: 0.5 µm, specific surface area: 5.9 m 2 / g, product of Ado-Matex Co., Ltd.), surface-treated with ”) was mixed and uniformly dispersed with a high-speed rotary mixer to produce a resin varnish. In the same manner as in Example 1, a resin sheet was produced.

Example 6

15 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 H1043" by Asai 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, 92 parts of radically polymerizable compounds ("OPE-2St" by Mitsubishi Gas Chemical Co., Ltd., number-average molecular weight 1200, toluene solution of 65 mass% of non volatile matters), radically polymerizable compound (Shin-Nakamura Chemical Industries) 30 parts of teacher-made "NK ester A-DOG", molecular weight 326), active ester type hardening | curing agent ("HPC8000-65T" made by DIC Corporation, toluene solution of 65 mass% of solid content), carbodiimide type hardening | curing agent (Nisshinbo chemical "V-03", 16 parts of active group equivalent weight, toluene solution of 50 mass% of solid content), hardening accelerator (N, N-dimethyl-4-aminopyridine (DMAP), MEK solution of 5 mass% of solid content) 6 Part, spherical silica (average particle diameter 0.3 micrometer, specific surface area 30.7) surface-treated with 1 part of polymerization initiators ("Perbutyl C" by Nichiyu Corp.), and a phenylamino silane coupling agent ("KBM573" by Shin-Etsu Chemical Co., Ltd.). M 2 / g, 200 parts of Denka Co., Ltd. "UFP-30") are mixed, and a high speed rotary mixer A resin sheet was produced by uniformly dispersing in the same manner as in Example 1 produce a resin varnish, and a.

Example 7

5 parts of biphenyl type epoxy resin ("NC3000L" by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 269), 10 parts of bisphenol AF type epoxy resin ("YL7760" by Mitsubishi Chemical Corporation, epoxy equivalent approximately 238), styrene-type elastomer (Asai casee Hydrogenated styrene thermoplastic elastomer "Toughtec P2000", styrene content 67%) 20 parts, Styrene-type elastomer (Epylene AT501 made from Daicel Co., Ltd. epoxidized styrene butadiene thermoplastic elastomer other than (C) component, styrene content) 40%) and 20 parts were dissolved by heating while stirring with 50 parts of toluene and 20 parts of MEK. After cooling to room temperature, 90 parts of radically polymerizable compounds ("NK ester A-DOG" by Shin-Nakamura Chemical Co., Ltd., molecular weight 326), active ester type hardening | curing agent ("HPC8000-65T" by DIC Corporation), 65 mass of solids are added here. 30 parts of toluene solution), 4 parts of triazine skeleton-containing phenol-based curing agent (DIC's "LA-3018-50P", 2-methoxypropanol solution of 50% of solid content of hydroxyl equivalent approximately 151), carbodiimide system 8 parts of hardening | curing agents ("V-03 by Nisshinbo Chemical Co., Ltd., active group equivalent about 216, toluene solution of 50 mass% of solid content), hardening accelerator (N, N-dimethyl-4-aminopyridine (DMAP), 5 mass% of solid content) Spherical silica (average particle diameter 0.3) surface-treated with 6 parts of MEK solution), 1 part of polymerization initiator ("Perbutyl C" manufactured by Nichiyu Corporation), and a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 200 micrometers, specific surface area of 30.7 m <2> / g, and 200 parts of "UFP-30" by Denka Co., Ltd. A resin sheet was produced by uniformly dispersing in the same manner as in Example 1 produce a resin varnish, and a.

Comparative Example 1

In Example 1, 3 parts of styrene-type elastomers (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" made from Acai 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 2

In Example 1,

1) 3 parts of styrene-based elastomers (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" manufactured by Acai Kasei Co., Ltd., styrene content 67%) are not used,

2) Without using 28 parts of active ester type hardening | curing agents (DEX company make "EXB9416-70BK", the methyl isobutyl ketone solution of 70 mass% of non volatile matters of about 330 active group equivalents),

3) 8 parts of triazine frame | skeleton containing phenolic hardening | curing agent (DIC company "LA-3018-50P", 2-methoxypropanol solution of 50% of solid content of hydroxyl equivalent approximately 151) carbodiimide type hardening | curing agent (Nisshinbo Chemical Co., Ltd.) To 16 parts of production "V-03", active group equivalent approximately 216, toluene solution of 50 mass% of solid content),

4) 1 part of polymerization initiators ("Percumyl P" by Nichiyu Corp.) was changed into 1 part of polymerization initiators ("Perbutyl C" by Nichiyu Corp.).

A resin varnish was produced in the same manner as in Example 1 except for the above matters. An attempt was made to produce a resin sheet from the resin varnish in the same manner as in Example 1, but production of the resin sheet was stopped because 10 or more aggregates of 1 mm or more were observed visually after dispersion by a high speed rotary mixer.

Comparative Example 3

In Example 6, 3 parts of styrene-type elastomers (hydrogenated styrene-based thermoplastic elastomer "Toughtec H1043" manufactured by Acai 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 6 except for the above matters.

In Examples 1-7, even if it does not contain (E) component-(H) component, although there was a difference in degree, it confirmed that it resulted in the same result as the said Example.

Claims (14)

(A) epoxy resin,
(B) curing agent,
(C) styrenic elastomers, and
(D) Resin having a radical polymerizable unsaturated group
Including,
The resin composition which is 61 mass% or more when content of the styrene unit in (C) component makes 100 mass% (C) component. 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 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 3000 or less. The resin composition of Claim 1 which further contains (E) an inorganic filler. The resin composition of Claim 5 which is 50 mass% or more, when content of (E) component makes 100 mass% the nonvolatile components in a resin composition. 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 formation of the insulation layer which has via hole whose tower diameter is 45 micrometers or less. The resin composition of Claim 1 whose thickness is for insulation layer formation of 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 1-11 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 1-11. The semiconductor device containing the printed wiring board of Claim 13.