KR20190120704A - Resin Composition - Google Patents

Abstract

A purpose of the present invention is to provide: a resin composition which can obtain a cured material which is low in dielectric tangent, excellent in smear removal property, and excellent in adhesiveness with a conductor layer; a resin sheet containing the resin composition; a printed wiring bard provided with an insulating layer formed by using the resin composition; and a semiconductor device. The resin compsition contains: (A) an epoxy resin; (B) an active ester-based curing agent; (C) (meth)acrylic acid ester; and (D) an inorgnaic filler, wherein a content of a component (D), when a nonvolatile component is 100 mass%, is 70 mass% or more, and if a value obtained by dividing the mass of a component (A) by an epoxy equivalent is a and a value obtained by dividing the mass of a component (B) by an active ester equivalent is b, a value of b/a is 1.3 or more.

Description

Resin Composition

The present invention relates to a resin composition. Moreover, it is related with the resin sheet, printed wiring board, and 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 insulating layer and a conductor layer alternately on an inner circuit board is known. The insulating layer is generally formed by curing the resin composition. For example, Patent Document 1 describes a resin composition containing a radical polymerizable compound (A), an epoxy resin (B), a curing agent (C), and a roughening component (D).

Japanese Laid-Open Patent Publication No. 2014-034580

Although many proposals of the resin composition suitable for formation of the insulating layer of an inner-layer circuit board are made including the resin composition described in patent document 1, the demand of the insulating layer with low dielectric tangent is increasing recently.

As a result of the present inventor's examination, it was found that the hardened | cured material of the resin composition containing the material which lowers dielectric loss tangent is hard to acquire adhesiveness with a conductor layer, etc., and also the smear removal property for ensuring conduction reliability is low. In recent years, in the manufacture of multilayer printed wiring boards, the cured product of the resin composition for forming the insulating layer is required to have sufficient adhesiveness and smear removal property in addition to low dielectric loss tangent, even in the miniaturization and densification of wiring. It is the present situation that is not reaching full satisfaction.

The subject of this invention is a resin composition which can obtain the hardened | cured material which is low in dielectric tangent, excellent in smear removal property, and excellent in adhesiveness with a conductor layer; Resin sheet containing the resin composition; Printed wiring board provided with the insulating layer formed using the said resin composition; And a semiconductor device.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve said subject, it contains (A) epoxy resin, (B) active ester type hardening | curing agent, (C) (meth) acrylic acid ester, and (D) inorganic filler in combination, And the (D) content of the inorganic filler and the resin composition which made the ratio (A) of the epoxy resin and the (B) active ester hardening | curing agent into the predetermined range found that the said subject can be solved, The present invention has been completed.

That is, this invention includes the following content.

[1] (A) epoxy resin,

(B) an active ester curing agent,

(C) (meth) acrylic acid ester, and

(D) inorganic filler

As a resin composition comprising

When content of (D) component makes non-volatile component in resin composition 100 mass%, it is 70 mass% or more,

The resin composition whose b / a is 1.3 or more when the value which divided the mass of (A) component by the epoxy equivalent is made into a, and the value which divided the mass of (B) component by the active ester group equivalent into b.

[2] The resin composition according to [1], in which the component (C) has two or more (meth) acryloyl groups per molecule.

[3] The resin composition according to [1] or [2], in which the component (C) has a cyclic structure.

[4] The resin composition according to any one of [1] to [3], in which the component (C) has a structure represented by the following formula (1).

(In formula (1), R <^1> and R <^4> represents acryloyl group or a methacryloyl group each independently, and R <^2> and R <^3> represent a bivalent coupling group each independently. Ring A is a bivalent cyclic group Indicates.)

[5] The resin composition according to any one of [1] to [4], in which the component (A) contains a liquid epoxy resin and a solid epoxy resin.

[6] The resin composition according to any one of [1] to [5], wherein the content of the component (D) is 75% 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], wherein the content of the component (C) is 1% by mass or more and 20% by mass or less when the resin component in the resin composition is 100% by mass.

[8] The resin composition according to any one of [1] to [7], which is used for insulation applications.

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

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

[11] The resin composition according to any one of [1] to [10], which is for sealing a semiconductor chip.

[12] A resin sheet comprising a support and a resin composition layer comprising the resin composition according to any one of [1] to [11], which is formed 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, resin composition which can obtain the hardened | cured material which is low in dielectric tangent, excellent in smear removal property, and excellent in adhesiveness with a conductor layer; Resin sheet containing the resin composition; Printed wiring board provided with the insulating layer formed using the said resin composition; And a semiconductor device.

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

[Resin composition]

The resin composition of this invention is a resin composition containing (A) epoxy resin, (B) active ester type hardening | curing agent, (C) (meth) acrylic acid ester, and (D) inorganic filler, Comprising: Content of (D) component is When the non-volatile component in the resin composition is 100 mass%, the mass obtained by dividing the mass of the component (A) by the epoxy equivalent is a, and the mass of the component (B) is the active ester group equivalent. When divided by b, b / a is 1.3 or more.

By using such a resin composition, it becomes possible to obtain the hardened | cured material which is low in dielectric tangent, excellent in smear removal property, and excellent in adhesiveness with a conductor layer.

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

<(A) Epoxy Resin>

As the (A) epoxy resin, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, 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-containing epoxy resin, Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthylene ether type epoxy resin , Trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. 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. Preferably it is 60 mass% or more, Especially preferably, it is 70 mass% or more.

The epoxy resin is a liquid epoxy resin (hereinafter sometimes referred to as "liquid epoxy resin") at a temperature of 20 ° C, and a solid epoxy resin (hereinafter may be referred to as a "solid epoxy resin") at a temperature of 20 ° C. There is. Although the resin composition may contain only liquid epoxy resin and may contain only solid epoxy resin as (A) epoxy resin, It is preferable to contain a liquid epoxy resin and solid epoxy resin in combination. By using a liquid epoxy resin and a solid epoxy resin in combination as (A) epoxy resin, sufficient flexibility is obtained when using it in the form of a resin sheet, or the breaking strength of the hardened | cured material of a resin composition can be improved. .

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

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 Phenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, and naphthol type epoxy resin and naphthalene type epoxy resin are more preferable. desirable.

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 Kagaku Corporation; "ESN485" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd. (naphthol novolac type epoxy resin); "YX4000H", "YX4000", "YL6121" (biphenyl type epoxy resin) by Mitsubishi Chemical Corporation; Mitsubishi Chemical Corporation "YX4000HK" (bixenol 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.

(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, Preferably 1: 1.5 to 1:15, particularly preferably 1: 2 to 1:10. When the ratio between the liquid epoxy resin and the solid epoxy resin is in this range, the desired effect of the present invention can be remarkably obtained. Moreover, when using normally in the form of a resin sheet, moderate adhesiveness arises. Moreover, when using normally in the form of a resin sheet, sufficient flexibility is obtained and handling property 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 50 g / eq. To 5000 g / eq., More preferably 50 g / eq. To 3000 g / eq., More preferably 80 g / 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.

(A) The weight average molecular weight (Mw) of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500 from a viewpoint which remarkably acquires the desired effect of this 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 sets the nonvolatile component in a resin composition to 100 mass% 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, 5 mass% or more, More preferably, it is 8 mass% or more. The upper limit of the content of the epoxy resin is preferably 25% by mass or less, more preferably 20% by mass or less, particularly preferably 15% 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) Active Ester Curing Agent>

The resin composition contains the (B) active ester curing agent. The use of an active ester curing agent usually results in a low dielectric loss tangent while poor smear removal. However, the resin composition of the present invention contains the component (C) and a predetermined amount of the component (D), and adjusts the amount ratio of the component (A) and the component (B) to be within a predetermined range, thereby lowering the dielectric tangent. In addition, it becomes possible to obtain the hardened | cured material excellent in smear removal property and adhesiveness.

(B) As an active ester type hardening | curing agent, generally two ester groups with high reaction activity, such as phenol esters, thiophenol esters, N-hydroxy amine ester, and ester of a heterocyclic hydroxy compound, are contained in 1 molecule. The compound which has the above is used preferably. It is preferable that the said active ester type hardening | curing agent is obtained by condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound, a hydroxy compound, and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound, a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid and pyromellitic acid. As the phenol compound or naphthol compound, for example, hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxy benzophenone, tetrahydroxy benzophenone, a 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.

Specifically, dicyclopentadiene type active ester curing agent, active ester curing agent containing naphthalene structure, active ester curing agent containing phenol of phenol novolac, and active ester curing agent containing benzomonide of phenol novolak A hardening | curing agent is preferable, Especially, the active ester type hardening | curing agent containing a naphthalene structure, the dicyclopentadiene type active ester type hardening | curing agent are more preferable, and the dicyclopentadiene type active ester type hardening | curing agent is still more preferable. As the dicyclopentadiene type active ester curing agent, an active ester curing agent containing a dicyclopentadiene type diphenol structure is preferable. "Dicyclopentadiene type diphenol structure" shows the bivalent structural unit which consists of phenylene dicyclopentylene phenylene.

(B) As a commercial item of an active ester hardening | curing agent, as an active ester hardening | curing agent containing a dicyclopentadiene type diphenol structure, "EXB9451" (made by DIC Corporation, active ester group equivalent 223 g / eq.), "EXB9460" ( DIC company make, active ester group equivalent 223 g / eq.), "EXB9460S" (DIC company make, active ester group equivalent 223 g / eq.), "HPC-8000-65T" (DIC company make, active ester group equivalent 223 g / eq.), "HPC-8000H-65TM" (made by DIC, active ester group equivalent of 224 g / eq.), "HPC8000L-65TM" (made by DIC, active ester group equivalent: 220 g / eq.), and naphthalene structure "EXB-8100L-65T" (Active ester group equivalent 234 g / eq.), "EXB8150-60T" (made by DIC Corporation, active ester group equivalent 226 g / eq.) As an active ester hardening | curing agent to make, "EXB9416" -70 BK "(made by DIC, active ester group equivalent 274 g / eq.)," PC1300-02 "(made by Air Water, active ester group equivalent 200 g / eq.), Phosphorus containing As an ester ester curing agent "EXB9401" (DIC Corporation, active ester group equivalent 307 g / eq.), Phenol novolac acetylide active ester curing agent "DC808" (Mitsubishi Chemical Corporation, active ester group equivalent 149 g / eq.) and "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and the like as an active ester curing agent which is a phenol phenol of phenol novolac. .

The active ester group equivalent of the (B) active ester curing agent is preferably 50 g / eq from the viewpoint of lowering the dielectric tangent and obtaining a cured product excellent in adhesion. To 500 g / eq., More preferably 50 g / eq. To 400 g / eq., More preferably 100 g / eq. To 300 g / eq. Active ester group equivalent is the mass of the active ester type hardening | curing agent containing 1 equivalent of active ester group.

The value which divided the mass of (A) component by the epoxy equivalent is made into a. This value "a" shows the equivalent number (eq.) Of the epoxy group which (A) component contains. In addition, the value which divided | diluted the mass of (B) component by the active ester group equivalent is set to b. This value "b" shows the equivalent number (eq.) Of the active ester group which (B) component contains. In this case, b / a is 1.3 or more, Preferably it is 1.35 or more, More preferably, it is 1.4 or more. Preferably an upper limit is 5 or less, More preferably, it is 3 or less, More preferably, it is 2 or less. By adjusting the ratio between the components (A) and (B) so that b / a is within this range, the dielectric tangent can be lowered and a cured product excellent in adhesion can be obtained. Here, when (A) component contains 2 or more types in a resin composition, said a is the value which totaled the value which divided the mass of each epoxy resin which exists in a resin composition by each epoxy equivalent. In addition, when (B) component contains 2 or more types, said b is the value which totaled the value which divided the mass of each active ester type hardening | curing agent which exists in a resin composition by each active ester group equivalent.

When the content of the (B) active ester curing agent is 100% by mass of the nonvolatile component in the resin composition, preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more. to be. Moreover, an upper limit becomes like this. Preferably it is 30 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 15 mass% or less. By making content of (B) component into such a range, dielectric loss tangent can be made low and the hardened | cured material excellent in adhesiveness can be obtained.

<(C) (meth) acrylic acid ester>

The resin composition contains (C) (meth) acrylic acid ester. By containing (C) (meth) acrylic acid ester in a resin composition, it becomes possible to make dielectric loss tangent low and to obtain the hardened | cured material excellent in smear removal property. By adjusting the ratio of the component (A) and the component (B) to be within a predetermined range, the dielectric tangent can be lowered and a cured product excellent in adhesion is obtained, but the smear removal property tends to be inferior. In it, it becomes possible to improve smear removal property by containing (C) component in a resin composition.

Here, the term "(meth) acrylic acid" includes acrylic acid and methacrylic acid, and combinations thereof.

(C) It is preferable that (meth) acrylic acid ester has two or more (meth) acryloyl groups per molecule from a viewpoint of making low dielectric loss tangent and obtaining hardened | cured material excellent in smear removal property. The term "(meth) acryloyl group" includes acryloyl group and methacryloyl group and combinations thereof.

(C) It is preferable that (meth) acrylic acid ester has a cyclic structure from a viewpoint of making dielectric hard tanning low and obtaining the hardened | cured material excellent in smear removal property. 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. Especially, it is preferable that it is a cyclic group containing an alicyclic structure from a viewpoint which remarkably acquires the desired effect of this invention.

From the viewpoint of remarkably obtaining the desired effect of the present invention, the divalent cyclic group is preferably at least 3 membered ring, more preferably at least 4 membered ring, still more preferably at least 5 membered ring, preferably at most 20 membered ring, more preferably. Preferably it is 15 or less ring, More preferably, it is 10 or less ring. Moreover, as a bivalent cyclic group, a monocyclic structure may be sufficient and a polycyclic structure may be sufficient.

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

Specific examples of the divalent cyclic group include the following divalent groups (i) to (xi). Especially, as a bivalent cyclic group, (x) or (xi) is preferable.

The divalent cyclic group may have a substituent. As such a substituent, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group , Oxo group, and the like, and an alkyl group is preferable.

The (meth) acryloyl 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. Examples of such alkylene groups include methylene groups, ethylene groups, propylene groups, butylene groups, pentylene groups, hexylene groups, 1,1-dimethylethylene groups, and the like. 1-dimethylethylene group is preferable. 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 heteroarylene group is preferable, and a C6-C10 arylene group or heteroarylene group is more preferable. As a bivalent coupling group, an alkylene group is preferable and a methylene group and 1, 1- dimethyl ethylene group are especially preferable.

(C) It is preferable that (meth) acrylic acid ester is represented by following formula (1).

(In formula (1), R <^1> and R <^4> represents acryloyl group or a methacryloyl group each independently, and R <^2> and R <^3> represent a bivalent coupling group each independently. Ring A is a bivalent cyclic group Indicates.)

R ¹ and R ⁴ each independently represent acryloyl group or methacryloyl group, and acryloyl group is preferable.

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

Hereinafter, although the specific example of (C) component is shown, this invention is not limited to this.

A commercial item may be used for (C) component, For example, "A-DOG" by the Shin-Nakamura Kagaku Kogyo Co., Ltd. "DCP-A" by the Kyogisha 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.

When content of (C) component makes the resin component in a resin composition 100 mass% from the viewpoint of remarkably obtaining the effect of this invention, Preferably it is 1 mass% or more, More preferably, it is 3 mass% or more, More Preferably it is 5 mass% or more. Preferably an upper limit is 20 mass% or less, More preferably, it is 18 mass% or less, More preferably, it is 15 mass% or less, or 10 mass% or less. The "resin component" of a resin composition means the component except the (D) inorganic filler among the non volatile components contained in a resin composition.

<(D) inorganic filler>

The resin composition contains the inorganic filler (D). (D) Content of an inorganic filler is 70 mass% or more, Preferably it is 73 mass% when the non-volatile component in a resin composition is 100 mass% from a viewpoint of making dielectric loss tangent low and improving smear removal property. As mentioned above, More preferably, it is 75 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. When content of an inorganic filler becomes 70 mass% or more, there exists a tendency for adhesiveness to fall easily, but since the resin composition of this invention adjusts the ratio of (A) component and (B) component so that it may become in a predetermined range, dielectric loss tangent It can be made low, and it becomes possible to obtain the hardened | cured material excellent in smear removal property and adhesiveness.

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

As a commercial item of the (D) inorganic filler, it is "UFP-30" by the Denka Kagaku Kogyo Co., Ltd .; "SP60-05" and "SP507-05" manufactured by Shinnitetsu Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" by Ado-Matex Corporation; "UFP-30" by the Denka Corporation; "Handwriting NSS-3N", "Handwriting NSS-4N", "Handwriting NSS-5N" manufactured by Tokuyama Co .; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" made by Ado-Matex Corporation; Etc. can be mentioned.

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

(D) The average particle diameter of an inorganic filler can be measured by the laser diffraction scattering method based on the Mie scattering theory. Specifically, the laser diffraction scattering particle diameter distribution measuring device can measure the particle diameter distribution of the inorganic filler on a volume basis and measure the median diameter as the average particle diameter. As a measurement sample, 100 mg of inorganic fillers and 10 g of methyl ethyl ketones were measured in a vial bottle, and what disperse | distributed for 10 minutes by the ultrasonic wave can be used. From the particle distribution obtained by using a laser diffraction type particle diameter distribution measuring device, the wavelength of the used light source was set to blue and red, and the particle size distribution of the volume standard of the inorganic filler (D) was measured by a flow cell method. The average particle diameter was calculated as the median diameter. As a laser diffraction type particle diameter distribution measuring apparatus, "LA-960" by Horiba Seisakusho Co., etc. is mentioned, for example.

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

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

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

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

The degree of surface treatment by a surface treating agent can be evaluated according to the amount of carbon per unit surface area of an inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and even more preferably 0.2 mg / m 2 or more. On the other hand, 1 mg / m <2> or less is preferable, 0.8 mg / m <2> or less is more preferable, 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 a sheet form.

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

<(E) Thermoplastic Resin>

The resin composition may further contain (E) thermoplastic resin as an arbitrary component other than the component mentioned above.

As the thermoplastic resin as the component (E), for example, a phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyether sulfone Resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin and the like. Especially, a phenoxy resin is preferable from a viewpoint of remarkably obtaining the desired effect of this invention, and a viewpoint of obtaining an insulating layer with a small surface roughness and especially excellent adhesiveness with a conductor layer. In addition, a thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

As the phenoxy resin, for example, bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton And phenoxy resins having one or more kinds of skeletons selected from the group consisting of anthracene skeletons, adamantane skeletons, terpene skeletons, and trimethylcyclohexane skeletons. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group and an epoxy group.

As a specific example of phenoxy resin, "1256" and "4250" by Mitsubishi Chemical Corporation (both bisphenol A frame | skeleton containing phenoxy resin); "YX8100" (Bisphenol S frame | skeleton containing phenoxy resin) by Mitsubishi Chemical Corporation; "YX6954" by Mitsubishi Chemical Corporation (bisphenol acetophenone skeleton containing phenoxy resin); "FX280" and "FX293" manufactured by Shinnitetsu Sumikin Kagaku Corporation; "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482" manufactured by Mitsubishi Chemical Corporation; Etc. can be mentioned.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, A polyvinyl butyral resin is preferable. As a specific example of polyvinyl acetal resin, "Denka butyral 4000-2", "Denka butyral 5000-A", "Denka butyral 6000-C" and "Denka butyral 6000-EP" by Denki Kagaku Kogyo Co., Ltd. make. ; Sekisui Kagaku Co., Ltd. Esrek BH series, BX series (for example BX-5Z), KS series (for example, KS-1), BL series, BM series; Etc. can be mentioned.

As a specific example of a polyimide resin, "Rica coat SN20" and "Rica coat PN20" by Shin-Nippon Rica company are mentioned. As a specific example of a polyimide resin, Linear polyimide (polyimide of Unexamined-Japanese-Patent No. 2006-37083) obtained by making bifunctional hydroxyl-group-end polybutadiene, a diisocyanate compound, and tetrabasic anhydride react also, polysiloxane Modified polyimides, such as a skeleton containing polyimide (polyimide of Unexamined-Japanese-Patent No. 2002-12667, Unexamined-Japanese-Patent No. 2000-319386, etc.), are mentioned.

As a specific example of polyamideimide resin, "Biromax HR11NN" and "Biromax HR16NN" by Toyobo Co., Ltd. are mentioned. Specific examples of the polyamideimide resin include modified polyamideimide such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Kasei Co., Ltd.

As a specific example of polyether sulfone resin, "PES5003P" by Sumitomo Kagaku Corporation, etc. are mentioned.

As an example of polyphenylene ether resin, Mitsubishi Gas Kagaku Co., Ltd. oligophenylene ether styrene resin "OPE-2St 1200" etc. are mentioned.

As a specific example of polysulfone resin, the polysulfone "P1700", "P3500", etc. by Solvay Advanced Polymers are mentioned.

(E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, and particularly preferably 20,000 or more, from the viewpoint of remarkably obtaining the desired effect of the present invention. 70,000 or less, More preferably, it is 60,000 or less, Especially preferably, it is 50,000 or less.

The content of the (E) thermoplastic resin is, from the viewpoint of remarkably obtaining the desired effect of the present invention, when the nonvolatile component in the resin composition is 100 mass%, preferably 0.1 mass% or more, and more preferably 0.2 mass% As mentioned above, More preferably, it is 0.3 mass% or more, Preferably it is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.

<(F) Curing agent>

In addition to the component mentioned above, the resin composition may contain (F) hardening | curing agent further as arbitrary components. However, the (B) active ester curing agent is not included in the (F) curing agent. (F) As a hardening | curing agent, a phenol type hardening | curing agent, a naphthol type hardening | curing agent, a benzoxazine type hardening | curing agent, a cyanate ester type hardening | curing agent, a carbodiimide type hardening | curing agent, etc. are mentioned, for example. Especially, it is preferable that (F) hardening | curing agent is any 1 or more types of a phenol type hardening | curing agent, a naphthol type hardening | curing agent, a cyanate ester type hardening | curing agent, and a carbodiimide type hardening | curing agent from a viewpoint of improving insulation reliability, It is more preferable to include. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

As a phenol type hardening | curing agent and a naphthol type hardening | curing agent, the phenol type hardening | curing agent which has a novolak structure, or the naphthol hardening | curing agent which has a novolak structure is preferable from a heat resistance and water resistance viewpoint. 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, "MEH-7700", "MEH-7810", "MEH-7851" by Meiwa Kasei Co., Ltd. "NHN" by Nippon Kayaku Co., Ltd., "CBN" , "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" by Shinnitetsu Sumikin Kagaku Corporation) And "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA3018-50P", "EXB-9500" by DIC Corporation, etc. are mentioned.

As a specific example of a benzoxazine type hardening | curing agent, "HFB2006M" by the Showa Kobunshi company, "P-d" by the 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'- methylene bis (2, 6-, for example) Dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4- Cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-sia Bifunctional cyanate resins such as natephenyl) thioether and bis (4-cyanatephenyl) ether, polyfunctional cyanate resins derived from phenol novolac and cresol novolak, and these cyanate resins are partially triazine Prepolymer etc. can be 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 and is trimer).

As a specific example of a carbodiimide-type hardening | curing agent, "V-03", "V-07", etc. by Nisshinbo Chemical Co., Ltd. are mentioned.

The value which divided the mass of (A) component by the epoxy equivalent is set to a, and the value which divided the mass of (F) component by the reactor equivalent is set to f. This value "f" shows the equivalent number (eq.) Of the reactor which (F) component contains. In this case, f / a becomes like this. Preferably it is 0.001 or more, More preferably, it is 0.005 or more, More preferably, it is 0.01 or more, Preferably it is 3 or less, More preferably, it is 2 or less, More preferably, it is 1 or less. Here, the reactor of a hardening | curing agent is an active hydroxyl group etc., and changes with kinds of hardening | curing agent. When 2 or more types of (F) components are contained in a resin composition, said f is the value which totaled the value which divided the mass of each (F) component which exists in a resin composition by the reactor equivalent, with respect to all (F) components. By making the ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition improves more.

The content of the (F) curing agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of remarkably obtaining the desired effect of the present invention. More preferably, it is 0.3 mass% or more. Preferably an upper limit is 5 mass% or less, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.

The value obtained by dividing the mass of component (A) by the epoxy equivalent is a, the value of the component (B) divided by the active ester group equivalent is b, and the value of the component (F) divided by the reactor equivalent is f (B + f) / a becomes like this. Preferably it is 1.1 or more, More preferably, it is 1.3 or more, More preferably, it is 1.5 or more. Preferably an upper limit is 5 or less, More preferably, it is 3 or less, More preferably, it is 2 or less. By adjusting the ratio of (A) component, (B) component and (F) component so that (b + f) / a falls within such a range, the cured product excellent in smear removal property and adhesiveness can be made low in dielectric loss tangent. It becomes possible to obtain.

<(G) Curing Accelerator>

The resin composition may further contain the (G) hardening accelerator as an arbitrary 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, and 1,8. -Diazabicyclo (5,4,0) -undecene, and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

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

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

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

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

(G) When content of the hardening accelerator makes the nonvolatile component in a resin composition 100 mass% from a viewpoint which remarkably acquires the desired effect of this invention, Preferably it is 0.01 mass% or more, More preferably, 0.03 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 (meth) acryloyl group in the component (C). (H) A polymerization initiator may be used individually by 1 type, or may use two or more types together.

(H) As a polymerization initiator, for example, t-butyl cumyl peroxide, t-butyl peroxy acetate, (alpha), (alpha) '-di (t-butyl peroxy) diisopropyl benzene, t-butyl peroxy laurate 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 Co., Ltd. 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 a viewpoint which remarkably acquires the desired effect of this invention, Preferably it is 0.01 mass% or more, More preferably, it is 0.03 mass% As mentioned above, More preferably, it is 0.05 mass% or more, Preferably it is 0.5 mass% or less, More preferably, it is 0.3 mass% or less, More preferably, it is 0.1 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, Organic filler; Resin additives such as thickeners, antifoaming agents, leveling agents and adhesion imparting agents; Etc. can be 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 the resin composition>

The hardened | cured material which thermosetted the resin composition for 30 minutes at 130 degreeC after that for 30 minutes shows the characteristic which is excellent in smear removal property. Therefore, when the via hole is formed in the cured product, an insulating layer having a maximum smear length of less than 5 mu m in the bottom of the via hole is formed. Smear removal property can be measured by 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 which is excellent in adhesiveness (fill strength) with a plating conductor layer. Therefore, the said hardened | cured material forms the insulating layer excellent in adhesiveness with a plating conductor layer. As adhesive strength with a plating conductor layer, Preferably it is 0.2 kgf / cm or more, More preferably, it is 0.3 kgf / cm or more, More preferably, it is 0.4 kgf / cm or more. On the other hand, the upper limit of the adhesion strength is not particularly limited, but may be 5 kgf / cm or less. Evaluation of the adhesive strength with said plating conductor layer can be measured in accordance with the method as described in the Example mentioned later.

The hardened | cured material which thermosetted the resin composition at 200 degreeC for 90 minutes shows the characteristic that dielectric loss tangent is low. 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 0.004 or less and 0.003 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 said dielectric loss tangent can be measured according to 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 excellent in smear removal property and adhesive force. Therefore, the resin composition of this invention can be used suitably as a resin composition of insulation use. Specifically, it can be suitably used as a resin composition (resin composition for forming insulation layer for forming 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.

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, a redistribution layer may be further formed on the sealing layer.

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

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

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

(4) Process of peeling a base material and a temporarily fixed film from a semiconductor chip,

(5) a step of forming a rewiring forming layer as an insulating layer on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off, and

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

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

[Resin Sheet]

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

The thickness of the resin composition layer is preferably 50 µm or less, more preferably 40 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, it is 30 micrometers or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, 5 micrometers or more, 10 micrometers or more can be made.

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

When using the film which consists of plastic materials as a support body, as a plastics material, for example, polyethylene terephthalate (it may abbreviate as "PET" hereafter), and polyethylene naphthalate (hereinafter abbreviated as "PEN"). Polyester, polycarbonate (hereinafter sometimes referred to as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. are mentioned. Especially, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using metal foil as a support body, copper foil, aluminum foil etc. are mentioned as metal foil, for example, copper foil is preferable. As copper foil, the foil which consists of a single metal of copper may be used, and the 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. .

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

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

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

In one embodiment, the resin sheet may further contain other layers as needed. As such another layer, the protective film etc. which conformed to the support body formed 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 are mentioned, for example. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating | stacking a protective film, adhesion | attachment and a scratch of dust etc. to the surface of a resin composition layer can be suppressed.

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

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

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

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

[Printed wiring board]

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

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

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

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

The "inner layer substrate" used in the step (I) is a member that becomes a substrate of a printed wiring board. For example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene And ether substrates. 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 side or both sides of the substrate may be referred to as an "inner layer circuit board". Moreover, when manufacturing a printed wiring board, the intermediate | middle manufacture to which the insulation layer and / or conductor layer should be formed further is also included in the "inner layer board" said by this invention. In the case where the printed wiring board is a circuit board with built-in parts, an inner layer board with built-in parts 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 the heat-compression member directly to the resin sheet, but to press the elastic material such as heat-resistant rubber in between so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

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

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

After lamination, 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 | stacking and smoothing process may be performed continuously using 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).

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

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

Process (IV) is a process of roughening an insulating layer. Usually, smear removal is also performed in this process (IV). The procedure and conditions of the roughening process are not particularly limited, and known procedures and conditions usually used when forming the insulating layer of a printed wiring board can be adopted. For example, the swelling treatment with the swelling liquid, the roughening treatment with the oxidizing agent, and the neutralization treatment with the neutralizing liquid can be performed in this order to roughen the insulating layer. Although it does not specifically limit as a swelling liquid used for a roughening process, Alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include "Swelling Deep Securigans P" manufactured by Atotech Japan, "Swelling Deep Securigans SBU", and the like. Although the swelling process by a swelling liquid is not specifically limited, For example, it can be performed by immersing an insulating layer for 1 to 20 minutes in 30 degreeC-90 degreeC swelling liquid. It is preferable to immerse an insulating layer for 5 to 15 minutes in 40 degreeC-80 degreeC swelling liquid from a viewpoint of suppressing swelling of resin of an insulating layer to a suitable level. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. It is preferable to perform roughening processing by oxidizing agents, such as alkaline permanganic acid solution, by immersing an insulating layer for 10 to 30 minutes in the oxidizing agent solution heated to 60 to 100 degreeC. Moreover, as for the density | concentration of the permanganate in alkaline permanganate solution, 5-10 mass% is preferable. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, As a commercial item, "Reduction solution security P by the Atotech Japan company" is mentioned, for example. The treatment with the neutralizing liquid can be performed by immersing the treated surface on which the roughening treatment with the oxidizing agent is applied in the neutralizing liquid at 30 ° C. to 80 ° C. for 5 minutes to 30 minutes. In view of workability, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralizing liquid at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, by plating on the surface of an insulating layer by conventionally well-known techniques, such as a semiadditive method and a full additive method, the conductor layer which has a desired wiring pattern can be formed, and from a viewpoint of the simplicity of manufacture, a 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 the insulating layer by electroless plating. Subsequently, a mask pattern for exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. After the metal layer is formed by electroplating on the exposed plating seed layer, the mask pattern is removed. Thereafter, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

[Semiconductor Device]

The semiconductor device of this invention contains the printed wiring board of this invention. The semiconductor device of this invention can be manufactured using the printed wiring board of this invention.

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

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

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, 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 a bumpless build-up layer (BBUL)" means "the mounting method which embeds a semiconductor chip in the recessed part of a printed wiring board, and connects the semiconductor chip and the wiring on a printed wiring board."

EXAMPLE

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

Example 1

10 parts of bisphenol-type epoxy resins ("ZX1059" made by Shin-Nitetsu Sumikin Kagaku Co., Ltd., 1: 1 mixed product of bisphenol A type and bisphenol F type, epoxy equivalent 169 g / eq), and naphthol type epoxy resin (Shin-Nitetsu Smykin) 50 parts of Kagaku Corporation "ESN475V" and epoxy equivalent weight of about 330 g / eq.) Were melt | dissolved by stirring, stirring 40 parts of solvent naphtha. This was cooled to room temperature and the dissolution composition of the epoxy resin was prepared.

Phenolic system which has 5 parts of phenoxy resins ("YX7553BH30" by Mitsubishi Kagaku Co., Ltd., 1: 1 solution of MEK and cyclohexanone of 30 mass% of non volatile matters), a triazine frame | skeleton, and novolak structure to the dissolution composition of this epoxy resin. 5 parts of hardening | curing agents ("LA-3018-50P" by DIC Corporation, active group equivalent approximately 151 g / eq., Non-volatile content 50% 2-methoxypropanol solution), active ester type hardening | curing agent (DIC company "HPC-8000-65T , 223 g / eq. Of active group equivalent, 110 parts of toluene solution of 65 mass% of non volatile matter, 15 parts of (meth) acrylic acid ester (A-DOG, Shin-Nakamura Kagaku Co., Ltd.), a hardening accelerator (1-benzyl-2-) Phenylimidazole (1B2PZ), 5 parts of non-volatile matter 10% by mass MEK solution), 2 parts of perbutyl P (manufactured by Nichi Oil, MEK solution of 20% non-volatile content) as a polymerization initiator, amine alkoxysilane compound (Shin-Etsuka Spherical Silica (average particle diameter: 0.5 µm, specific surface area: 5.9 m 2 / g, adomatics) surface treated with Kakukogyo Co., Ltd. Prepared "SO-C2"), 510 parts of cyclohexanone, 10 parts MEK 10 parts mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

A-DOG has a structure shown below.

As a support body, the polyethylene terephthalate (PET) film ("AL5" by Lintec company, thickness 38 micrometers) provided with the release layer was prepared. On the release layer of this support body, said resin varnish was apply | coated uniformly so that the thickness of the resin composition layer after drying might be 25 micrometers. Then, the resin varnish was dried at 80 degreeC-100 degreeC (average 90 degreeC) for 6 minutes, and the resin sheet containing a support body and a resin composition layer was obtained.

Example 2

In Example 1, 110 parts of an active ester system hardener ("HPC-8000-65T" by DIC Corporation, about 223 g / eq. Of active group equivalents, a toluene solution of 65 mass% of non volatile matters), an active ester system hardener (made by DIC Corporation) 110 parts of "HPC-8000L-65TM", an active group equivalent of 220 g / eq., And a toluene-MEK mixed solution having a nonvolatile content of 65%). A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

Example 3

In Example 1, 110 parts of an active ester system hardener ("HPC-8000-65T" by DIC Corporation, about 223 g / eq. Of active group equivalents, a toluene solution of 65 mass% of non volatile matters), an active ester system hardener (made by DIC Corporation) 120 parts of "EXB-8150-60T", the active group equivalent 230g / eq., And the toluene solution of 60% of non volatile matters) were changed. A resin varnish and a resin sheet were produced in the same manner as in Example 1 except for the above matters.

Example 4

In Example 3, 15 parts of acrylic ester (A-DOG, manufactured by Shin-Nakamura Kagaku Co., Ltd.) was changed to 15 parts of acrylic ester (DCP-A, manufactured by Kyogisha Co., Ltd.). A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above matters.

DCP-A has a structure shown below.

Example 5

In Example 4, the amount of the active ester curing agent (“EXB-8150-60T” manufactured by DIC Corporation, active group equivalent 230 g / eq., Toluene solution having a nonvolatile content of 60%) was changed from 120 parts to 140 parts, and the amine system The amount of spherical silica (average particle diameter: 0.5 µm, manufactured by Adomattex Co., Ltd., "SO-C2" manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 510 parts to 520 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 4 except for the above matters.

Comparative Example 1

In Example 3, spherical silica (average particles) surface-treated with an amine alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) without using 15 parts of acrylic ester (A-DOG, manufactured by Shin-Nakamura Kagaku Co., Ltd.). 0.5 micrometer in diameter, and the amount of "DO-C2" by Ado-Matex Corporation were changed from 510 parts to 480 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above matters.

Comparative Example 2

In Example 3, the amount of the active ester curing agent (“EXB-8150-60T” manufactured by DIC Corporation, active group equivalent 230 g / eq., Toluene solution having a nonvolatile content of 60%) was changed from 120 parts to 80 parts, and the amine type The amount of spherical silica (average particle diameter: 0.5 µm, manufactured by Ado-Matex, Inc., "SO-C2" manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 510 parts to 450 parts. A resin varnish and a resin sheet were produced in the same manner as in Example 3 except for the above matters.

[Evaluation of Smear Removability and Plating Peel Strength]

<Production of Evaluation Board A>

(1) background processing of embedded substrate

As an inner layer board | substrate, the glass cloth base material epoxy resin double-sided copper clad laminated board (copper foil thickness 18 micrometers, board | substrate thickness 0.8mm, Panasonic Corporation "R1515A") which has copper foil on the surface was prepared. The copper foil of the surface of this inner layer board | substrate was etched by the etching amount of 1 micrometer using the microetching agent ("CZ8101" by Mex Corporation), and the roughening process was performed. Then, drying was performed at 190 degreeC for 30 minutes.

(2) Lamination and Curing of Resin Sheet

Inner layer board | substrate so that the resin composition layer may bond with the said inner layer board | substrate using the batch type vacuum pressurizing laminator (2 stage buildup laminator "CVP700" made by Nikko Materials) by using the resin sheet obtained by the Example and comparative example which were mentioned above. Laminated on both sides of the. This laminate was pressure-reduced for 30 seconds, and after making atmospheric pressure 13 hPa or less, it crimped | bonded for 30 second at the temperature of 100 degreeC, and the pressure of 0.74 Mpa.

Subsequently, the laminated resin sheet was heat press smoothed for 60 seconds at 100 degreeC and the pressure of 0.5 MPa under atmospheric pressure. Furthermore, this was put into 130 degreeC oven, and it heated for 30 minutes, Then, it transferred to 170 degreeC oven, and heated for 30 minutes.

(3) formation of via holes

Using a CO ₂ laser processing machine (LK-2K212 / 2C) manufactured by Via Mechanics Co., Ltd., the insulating layer was processed under a condition of pulse width of 3 μsec, output of 0.95 W, and the number of shots 3 at a frequency of 2000 Hz, and the top of the insulating layer surface A via hole having a diameter (diameter) of 50 µm and a diameter of 40 µm at the bottom surface of the insulating layer was formed. Moreover, the PET film was peeled after that.

(4) coordination treatment

The inner layer substrate was immersed at 60 ° C. for 10 minutes in the swelling deep security P, manufactured by Atotech Japan Co., which is a swelling liquid. Next, the blend solution of Ato Tech Japan Corporation Concentrate compact was dipped P (KMnO _4: aqueous solution of 40g / L: 60g / L, NaOH) at 80 ℃ 20 minutes. Finally, it was immersed for 5 minutes in 40 degreeC reduction solution Securigant P of Atotech Japan which is neutralization liquid. The obtained board | substrate was called evaluation board | substrate A.

<Residue Evaluation at the Bottom of Via Hole (Evaluation of Smear Removal)>

The circumference | surroundings of the bottom part of the via hole of the evaluation board | substrate A were observed with the scanning electron microscope (SEM), and the maximum smear length from the wall surface of the via hole bottom part was measured from the obtained image, and the following references | standards evaluated.

(Circle): Maximum smear length is less than 5 micrometers.

X: Maximum smear length is 5 micrometers or more.

<Measurement of Plating Peel Strength>

The evaluation board A, the electroless containing PdCl ₂ was immersed for 5 minutes at 40 ℃ in the plating solution, and was then immersed in an electroless copper plating solution for 20 minutes at 25 ℃ with. After heating at 150 degreeC for 30 minutes and performing an annealing process, an etching resist was formed and after the pattern formation by etching, copper sulfate electroplating was performed and the conductor layer of 30 micrometers thickness was formed. Next, the annealing process was performed at 200 degreeC for 60 minutes, and the obtained board | substrate was called evaluation board | substrate B.

A sheath of 10 mm in width and 150 mm in length is placed in the conductor layer of the evaluation board B, and this end is peeled off and picked up by a pick-up tool (manufactured by TS Co., Autocom Type Tester AC-50C-SL), at room temperature (25 ° C), The load (kgf / cm) when 100 mm was removed in the vertical direction at a speed of 50 mm / min was measured.

[Measurement of Dielectric Tangent]

The resin sheet obtained by each Example and each comparative example was heat-hardened at 190 degreeC for 90 minutes, the PET film was peeled off, and the sheet-like hardened | cured material was obtained. The cured product was cut into a test piece having a width of 2 mm and a length of 80 mm, and measured using a cavity resonance method using a cavity resonator perturbation dielectric constant measuring device CP521 manufactured by Kanto Ohio Denshi Kaihatsu Co., Ltd. and a network analyzer E8362B manufactured by Agilent Technologies. The dielectric loss tangent (tanδ) was measured at GHz. Two test pieces were measured and the average value was computed.

In the table, "a" represents the value obtained by dividing the mass of the component (A) by epoxy equivalent, and "b" represents the value obtained by dividing the mass of the component (B) by the active ester group equivalent, and "f" represents The value obtained by dividing the mass of the component (F) by the reactor equivalent. "Content of (C) component" shows content of (C) component when the resin component in a resin composition is made into 100 mass%, and "content of (D) component is 100 the non-volatile component in a resin composition. Content of (D) component in the case of mass% is shown.

In Examples 1-5, even if it did not contain (E) component-(H) component, although it differed in grade, it confirmed that it resulted in the same result as the said Example.

Claims (14)

(A) epoxy resin,
(B) an active ester curing agent,
(C) (meth) acrylic acid ester, and
(D) inorganic filler
As a resin composition comprising
When content of (D) component makes non-volatile component in resin composition 100 mass%, it is 70 mass% or more,
The resin composition whose b / a is 1.3 or more, when the value which divided | diluted the mass of (A) component by the epoxy equivalent was made into a, and the value which divided | diluted the mass of the component (B) by the active ester group equivalent into b. The resin composition of Claim 1 in which (C) component has two or more (meth) acryloyl groups per molecule. The resin composition of Claim 1 in which (C) component has a cyclic structure. The resin composition of Claim 1 in which (C) component has a structure represented by following formula (1).

(In formula (1), R <^1> and R <^4> represents acryloyl group or a methacryloyl group each independently, and R <^2> and R <^3> represent a bivalent coupling group each independently. Ring A is a bivalent cyclic group Indicates.) The resin composition of Claim 1 in which (A) component contains a liquid epoxy resin and a solid epoxy resin. The resin composition of Claim 1 whose content of (D) component is 75 mass% or more, when the non volatile component in a resin composition is 100 mass%. The resin composition of Claim 1 which is 1 mass% or more and 20 mass% or less when content of (C) component makes the resin component in a resin composition 100 mass%. The resin composition of Claim 1 used for insulation uses. 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 sealing of a semiconductor chip. The resin sheet containing the support body and the resin composition layer containing the resin composition of any one of Claims 1-11 formed 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.