TW201809125A - Resin composition - Google Patents

Abstract

The present invention provides a resin composition capable of realizing a thin layer insulating layer having a relatively low dielectric constant and a good adhesion to a conductor layer. The resin composition of the present invention comprises (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an organic filler.

Description

Resin composition

The present invention relates to a resin composition. Further, the present invention relates to a sheet-like laminated material containing the resin composition, a printed circuit board, a fingerprint authentication sensor, and a semiconductor device containing an insulating layer formed by a hardened material of the resin composition.

In recent years, due to the demand for miniaturization of electronic equipment, high-speed signals, and high-density wiring, thinner insulation layers have been required. In order to reduce the thickness of the insulating layer, it is necessary to reduce the dielectric constant in order to control the impedance.

In order to reduce the dielectric constant of the insulating layer, it is preferable to use a filler having a lower dielectric constant than fluororesin powder such as polytetrafluoroethylene (see Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-269530

[Summary of Invention]

However, the polytetrafluoroethylene described in Patent Document 1 has a problem in dispersibility due to its strong hydrophobicity. In addition, when the polytetrafluoroethylene particles are used to form the insulating layer, the dispersibility of the particles is insufficient, the melt viscosity becomes high, the use is difficult, and the adhesion between the insulating layer and the conductor layer may cause problems.

The problem to be solved by the present invention is to provide a resin composition that can provide an insulating layer with a thin layer having a low specific permittivity and excellent adhesion to a conductor layer.

As a result of careful examination of the above problems by the present inventors, it was found that by using (A) epoxy resin, (B) hardener, (C) fluorine atom-containing alkoxysilane compound, and (D) organic filler The above problems can be solved, and the present invention has been completed.

That is, the present invention includes the following.

[1] A resin composition containing (A) an epoxy resin, (B) a hardener, (C) a fluorine atom-containing alkoxysilane compound, and (D) an organic filler.

[2] The resin composition according to the item [1], wherein the average particle diameter of the component (D) is 0.05 μm to 5 μm.

[3] The resin composition according to the item [1] or [2], wherein the component (D) is a particle having a specific permittivity of 2.8 or less at a measurement frequency of 5.8 GHz.

[4] The resin composition according to any one of the above [1] to [3], wherein The component (D) is a particle containing a fluororesin.

[5] The resin composition according to any one of the above [1] to [4], wherein the number of fluorine atoms in one molecule of the component (C) is 1 to 10.

[6] The resin composition according to any one of the above [1] to [5], wherein the number of alkoxy groups in one molecule of the component (C) is 1 to 5.

[7] The resin composition according to any one of the above [1] to [6], wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane.

[8] The resin composition according to any one of the above [1] to [7], further containing (E) an inorganic filler.

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

[10] The resin composition according to any one of the above [1] to [9], which has a specific dielectric constant at a measurement frequency of 5.8 GHz of a hardened product formed by hardening the resin composition of 3.0 or less, from 25 ° C The average linear thermal expansion coefficient to 150 ° C is 55 ppm / ° C or less.

[11] The resin composition according to any one of the above [1] to [10], which is used for forming an insulating layer of a printed circuit board.

[12] The resin composition according to any one of the above [1] to [11], which is used for a build-up insulating layer of a printed circuit board.

[13] A sheet-like laminated material comprising the resin composition according to any one of [1] to [12].

[14] A sheet-like laminated material comprising a resin composition layer formed of the resin composition of any one of [1] to [12].

[15] The sheet-like laminated material according to the item [14], wherein the thickness of the resin composition layer is 30 μm or less.

[16] A printed circuit board comprising an insulating layer formed of a cured product of the resin composition of any one of [1] to [12].

[17] A fingerprint authentication sensor including an insulating layer formed of a cured product of the resin composition of any one of [1] to [12].

[18] A semiconductor device including the printed circuit board of [16] or the fingerprint authentication sensor of [17].

According to the present invention, it is possible to provide a resin composition which can provide an insulating layer having a low specific dielectric constant and a thin layer having excellent adhesion to a conductor layer.

1‧‧‧Fingerprint authentication sensor

2‧‧‧printed circuit board

3‧‧‧ Insulation

4‧‧‧ insulation coating

5‧‧‧ metal electrode

[Fig. 1] Fig. 1 is a sectional view schematically showing a fingerprint authentication sensor of the present invention.

[Form of Implementing Invention]

Hereinafter, the resin composition of the present invention, a sheet-like laminated material containing the resin composition, a printed circuit board, a fingerprint authentication sensor, and a semiconductor device will be described in detail.

[Resin composition]

The resin composition of the present invention contains (A) an epoxy resin, (B) a hardener, (C) a fluorine atom-containing alkoxysilane compound, and (D) an organic filler.

Hereinafter, each component contained in the resin composition of this invention is demonstrated in detail.

<(A) epoxy resin>

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, dicyclopentadiene epoxy resin, and triphenol. Type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type Epoxy resin, epoxypropylamine epoxy resin, epoxypropylester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, Diene epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexanedimethanol type epoxy resin, naphthyl ether type epoxy resin, trihydroxy Methyl-type epoxy resin, tetraphenylethane-type epoxy resin, bisxylenol-type epoxy resin, and the like. The epoxy resin may be used singly or in combination of two or more kinds. The component (A) is preferably one or more selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, and a biphenyl epoxy resin.

Epoxy resin contains two or more rings in one molecule An epoxy resin is preferred. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C (hereinafter referred to as a "liquid epoxy resin") and an epoxy group having three or more epoxy groups in one molecule are included. An epoxy resin that is solid at a temperature of 20 ° C (hereinafter referred to as "solid epoxy resin") is preferred. By using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the fracture strength of the hardened | cured material of a resin composition can also be improved.

The liquid epoxy resin is preferably a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AF epoxy resin, a naphthalene epoxy resin, an epoxy propyl ester epoxy resin, or an epoxy resin. Propylamine epoxy resin, phenol novolac epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol epoxy resin, epoxypropylamine epoxy resin, and butylamine epoxy resin Diene-structured epoxy resins are more preferably epoxypropylamine epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol AF epoxy resin, and naphthalene epoxy resin. . Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene-type epoxy resin) made by DIC, and "828US" and "jER828EL" made by Mitsubishi Chemical Corporation. (Bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (epoxypropylamine type) Epoxy resin), "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) made by Nippon Steel & Sumitomo Chemical Co., Ltd., "EX-721" (glycidyl epoxy resin) manufactured by Nagasechemtex (stock), "CELLOXID2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL (stock), "PB-3600" (Epoxy resin with butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-epoxypropylcyclohexane) made by Nippon Steel Chemical Co., Ltd., and Mitsubishi Chemical Co., Ltd. "630LSD" (epoxypropylamine type epoxy resin), etc. These can be used individually by 1 type or in combination of 2 or more types.

The solid epoxy resin is preferably a naphthalene type 4-functional epoxy resin, a cresol novolac type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol type epoxy resin, Benzene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, tetraphenylethane type epoxy resin, more preferably naphthalene type 4-functional epoxy resin, naphthalene Phenol-type epoxy resin and biphenyl-type epoxy resin. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type 4-functional epoxy resin), " "N-690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP -7200HH "," HP-7200H "," EXA-7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(Dnaphthyl ether epoxy Resin), "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" made by Nippon Kayaku Co., Ltd. , "NC3100" (Biphenyl type epoxy resin), `` ESN475V '' (naphthalene type epoxy resin), `` ESN485 '' (naphthol novolac type epoxy resin) made by Nippon Steel & Sumitomo Chemical Co., Ltd., and Mitsubishi Chemical (stock) company "YX4000H", "YL6121" (biphenyl epoxy resin), "YX4000HK" (bisxylenol epoxy resin), "YX8800" (anthracene epoxy resin), made by Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (茀 -type epoxy resin), manufactured by Mitsubishi Chemical Co., Ltd. "JER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), and the like. These can be used individually by 1 type or in combination of 2 or more types.

When the epoxy resin is a combination of a liquid epoxy resin and a solid epoxy resin, their weight ratios (liquid epoxy resin: solid epoxy resin) are expressed by mass ratio, preferably 1: 0.1 ~ 1:15 range. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin within this range, i) can be used in the form of a resin sheet, which can bring moderate adhesion, ii) can be used in the form of a resin sheet In this case, sufficient flexibility can be obtained to improve workability, and iii) effects such as a hardened material having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is expressed by mass ratio, and more preferably 1: The range is from 0.3 to 1:10, more preferably from 1: 0.6 to 1: 8, and even more preferably from 1: 1.5 to 1: 5. As the epoxy resin, only a solid epoxy resin may be used.

The content of epoxy resin in the resin composition can be obtained from From the viewpoint of an insulating layer showing good mechanical strength and insulation reliability, it is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, and still more preferably 10% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention can be exhibited, and is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or 25% by mass. the following.

In the present invention, the content of each component in the resin composition is the value when the non-volatile component in the resin composition is 100% by mass unless specifically stated otherwise.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1,000. Within this range, an insulating layer with sufficient cross-linking density of the hardened material and a small surface roughness can be brought. The epoxy equivalent can be measured in accordance with JIS K7236 and is the mass of a resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 150 to 3000, and still more preferably 200 to 1500. Here, the weight average molecular weight of an epoxy resin is a polystyrene conversion weight average molecular weight measured by the gel permeation chromatography (GPC) method.

<(B) Hardener>

The hardener is not particularly limited as long as it has a function of hardening the epoxy resin, and examples thereof include a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, a benzoxazine-based hardener, and a cyanate ester. Based hardener, and carbodiimide based hardener. Hardener can be used alone or in combination of 2 or more on. The component (B) is preferably one or more selected from a phenol-based hardener, a naphthol-based hardener, an active ester-based hardener, and a cyanate-based hardener.

From the viewpoints of heat resistance and water resistance, the phenol-based hardener and the naphthol-based hardener are preferably a phenol-based hardener having a novolac structure or a naphthol-based hardener having a novolac structure. From the viewpoint of adhesion with the conductor layer, a nitrogen-containing phenol-based hardener is preferred, and a phenol-based hardener containing a triazine skeleton is more preferred. Among these, a phenol novolak hardener containing a triazine skeleton is preferred from the viewpoint of satisfying high heat resistance, water resistance, and adhesion to the conductor layer.

Specific examples of the phenol-based hardener and naphthol-based hardener include, for example, "MEH-7700", "MEH-7810", "MEH-7851", manufactured by Nippon Kasei Kasei Co., Ltd., and manufactured by Nippon Kayakusho Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN375", " "SN395", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc. of the DIC system.

From the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, an active ester-based hardener is preferred. The active ester-based hardener is not particularly limited. Generally, it is preferable to use two or more molecules in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds. Highly reactive ester-based compounds. The active ester-based hardener is obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. Especially from improving From the viewpoint of heat resistance, an active ester-based hardener obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based hardener obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenol-based, methylated bisphenol A, methylated bisphenol F, and methylation. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene , 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, resorcinol, benzenetriol, dicyclopentadiene-type diphenol compound, phenol Novolac, etc. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetic acid compound of a phenol novolac, and an active ester compound containing a phenolic novolac compound. Active ester compounds are preferred, and among them, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit formed of phenylene-dicyclopentyl-phenylene.

Commercially available products of active ester-based hardeners, which contain dicyclopentadiene-type diphenol-containing active ester compounds, include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC (stock)), active ester compounds containing a naphthalene structure, and "EXB9416-70BK" (manufactured by DIC (stock)), including phenol novolac Examples of the active ester compounds of ethyl acetate are "DC808" (manufactured by Mitsubishi Chemical Corporation), and the active ester compounds of benzyl compounds containing phenol novolac are "YLH1026" (manufactured by Mitsubishi Chemical Corporation) Examples of the active ester-based hardener for the acetic acid compound of phenol novolak include "DC808" (manufactured by Mitsubishi Chemical Corporation), and the active ester-based hardener for the benzoic acid compound of phenol novolak includes "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation), etc.

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

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), and 4,4'-subline. Methylbis (2,6-dimethylphenylcyanate), 4,4'-ethylenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis ( 4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethylphenyl) methane, 1,3- 2 of bis (4-cyanatephenyl-1- (methylethylene)) benzene, bis (4-cyanatephenyl) sulfide, and bis (4-cyanatephenyl) ether Functional cyanate resins, polyfunctional cyanate resins derived from phenol novolacs, cresol novolacs, etc., prepolymers in which some of these cyanate resins are triazinated, and the like. Cyanate ester-based hardening Specific examples of the agent include "PT30" and "PT60" (both phenol novolac-type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A dicyanide) manufactured by Lonza Japan Co., Ltd. Prepolymers of which a part or all of the acid esters are triazinated terpolymers) and the like.

Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" made by Nishinbo Chemical Co., Ltd.

The ratio of the amount of the epoxy resin to the hardener is [the total number of epoxy groups of the epoxy resin]: [the total number of the reactive groups of the hardener]. The ratio is preferably in the range of 1: 0.01 to 1: 2. It is more preferably 1: 0.015 to 1: 1.5, and even more preferably 1: 0.02 to 1: 1. Here, the reactive group of the hardener refers to an active hydroxyl group, an active ester group, and the like, and it varies depending on the type of the hardener. In addition, the total number of epoxy groups of an epoxy resin refers to a value obtained by dividing the solid content mass of each epoxy resin by the value of the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the hardener refers to For all the hardeners, the value obtained by dividing the mass of the solid content of each hardener by the equivalent of the reactive group equivalent. By setting the ratio of the amount of the epoxy resin to the hardener within this range, the heat resistance of the hardened product of the resin composition is further improved.

In one embodiment, the resin composition includes the (A) epoxy resin and (B) hardener. The resin composition contains a mixture of a liquid epoxy resin and a solid epoxy resin (A) as an epoxy resin (a mass ratio of the liquid epoxy resin to the solid epoxy resin, preferably 1: 0.1 to 1) : 15, more preferably 1: 0.3 ~ 1: 10, and even more preferably 1: 0.6 ~ 1: 8), and contains (B) a hardener selected from the group consisting of a phenol-based hardener, a naphthol-based hardener, and an activity Ester hardener and cyanate ester hardener Above (preferably one or more selected from the group consisting of a phenol-based hardener, a naphthol-based hardener, and an active ester-based hardener).

The content of the hardener in the resin composition is not particularly limited, but it is preferably 30% by mass or less, more preferably 25% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less. The lower limit is not particularly limited, but is preferably 0.5% by mass or more.

<(C) fluorine-containing alkoxysilane compound>

The resin composition of the present invention contains (C) a fluorine atom-containing alkoxysilane compound. By containing the component (C), the dispersibility of the component (D) described later is increased, the melt viscosity of the resin composition layer is reduced, and the adhesion between the insulating layer and the conductor layer formed by the hardening of the resin composition can be improved. (C) The component has the effect of strengthening the interface of dissimilar materials, so it has high resistance to oxidants (degumming solution). By containing the component (C), the thickness of the insulating layer is reduced, and the adhesion between the insulating layer and the conductor layer can be improved.

(C) component From the viewpoint of improving the resistance to the oxidizing agent for roughening treatment, the number of fluorine atoms in 1 molecule of the component (C) is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

The component (C) preferably has a fluorinated alkyl group from the viewpoint of improving the resistance to an oxidizing agent for roughening treatment, and the fluorinated alkyl group preferably has a fluorine atom at a terminal. The fluorinated alkyl is preferably a fluorinated alkyl having 1 to 20 carbon atoms, more preferably a fluorinated alkyl having 1 to 10 carbon atoms, and even more preferably a fluorinated alkyl having 1 to 6 carbon atoms. Examples of such a fluorinated alkyl group include -CF ₃ , -CH ₂ CF ₃ , -CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₃ , -CH (CF ₃ ) ₂ , -CH ₂ CH ₂ CH ₂ CF ₃ , -CH ₂ CH (CF ₃ ) ₂ , -C (CF ₃ ) ₃ and the like, preferably -CH ₂ CH ₂ CF ₃ .

From the viewpoint of improving reactivity, the number of alkoxy groups in one molecule of the component (C) is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2 to 3.

From the viewpoint of improving reactivity, the alkoxy group in the component (C) is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably carbon. Alkoxy having 1 to 6 atoms. Examples of such an alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, s-butoxy, isobutoxy, t-butoxy, and pentoxy , Hexyloxy, heptyloxy, octyloxy, nonyloxy, and decyloxy, preferably methoxy.

The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, -OC _1-6 alkyl, -N (C _1-6 alkyl) ₂ , C _1-6 alkyl, C _6-10 aryl,- NH ₂ , -CN, -C (O) OC _1-6 alkyl, -COOH, -C (O) H, -NO ₂ and the like.

Here, the term "C _pq " (p and q are positive integers and satisfy p <q.) Means that the number of carbon atoms of the organic group described later in this term is p to q. For example, the description of "C _1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms.

The above-mentioned substituent may further have a substituent (hereinafter may be referred to as a "secondary substituent"). When a secondary substituent is not specifically mentioned, the same thing as the said substituent can be used.

The molecular weight of the component (C) is preferably 50 to 2,000, more preferably 75 to 100, and still more preferably 100 to 500 from the viewpoint of improving compatibility.

Among these, the component (C) includes 3,3,3-trifluoropropyltrimethoxysilane, an alkoxysilane compound containing a perfluoro (poly) ether group, and the like. These can be used individually by 1 type or in combination of 2 or more types. Among these, the (C) component is preferably 3,3,3-trifluoropropyltrimethoxysilane. (C) As a component, you may use a commercial item, For example, "KBM-7103" and "optool DSX" by Shin-Etsu Chemical Industry Co., Ltd. are mentioned.

The component (C) may be contained alone in the resin composition of the present invention, and a part or all of the component (C) may be contained in the resin composition as a surface treatment agent for (E) an inorganic filler (described later).

The content of the component (C) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and still more preferably 0.2% by mass or more. The upper limit is not particularly limited, but is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 6% by mass or less.

<(D) Organic Filler>

The resin composition of the present invention contains (D) an organic filler ((D) component). In the present invention, the component (D) is a component that lowers the specific permittivity of the insulating layer obtained by curing the resin composition (reducing the dielectric constant of the insulating layer). From the viewpoint of lowering the dielectric constant of the insulating layer, particles having a specific dielectric constant of 3.2 or less at a measurement frequency of 5.8 GHz are preferred for the (D) component, and more preferable than particles having a dielectric constant of 3.0 or less. Particles with a specific permittivity of 2.8 or less are more preferable. The lower limit of the specific dielectric constant of the (D) component is not particularly limited, and may be 1.1 or more.

(D) The particle diameter of the component is not particularly limited. From the viewpoint of excellent dispersibility, the average particle diameter is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. The lower limit of the average particle diameter of the component (D) is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.08 μm or more, and still more preferably 0.10 μm or more. Therefore, the particles of the component (D) have an average particle diameter of 0.05 μm to 5 μm, more preferably 0.08 μm to 4 μm, and even more preferably 0.10 μm to 3 μm.

The component (D) is not particularly limited as long as it reduces the dielectric constant of the insulating layer, and examples thereof include a member selected from the group consisting of fluororesin, fluororubber, polyethylene, polypropylene, polystyrene, polycarbonate, and hafnium. Ethylene resin, addition copolymerization resin with olefins, polyphenylene ether, bismaleimide. Triazine. Resin, polyetherimide, polyimide, polyetheretherketone, and a liquid crystal polymer. Among these, fluororesin-containing particles are preferred.

Examples of the fluororesin include polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), perfluoroethylene propylene copolymer (FEP), ethylene.tetrafluoroethylene copolymer (ETFE), and tetrafluoroethylene-perfluoro Dioxolene copolymer (TFE / PDD), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyfluorinated vinyl ( PVF) and so on. These resins can be used singly or in combination of two or more kinds. From the viewpoint of reducing the dielectric constant of the insulating layer, PTFE is preferred. The weight average molecular weight of the PTFE particles is preferably 5,000,000 or less, more preferably 4,000,000 or less, and even more preferably 3,000,000 or less.

Specific examples of PTFE include DAIKIN INDUSTRIES (RuburonL-2), DAIKIN INDUSTRIES (ruburonL-5), Drukinon-5-5 (DAIKIN INDUSTRIES), FluonPTFE L-170JE, Asahi Glass (share) "FluonPTFE L-172JE", Asahi Glass (FluonPTFE L-173JE), "KTL-500F" (KTL-500F), "KTL-2N" (KTL-2N), "KTL-" 1N ", Mitsui. Dupont Fluorochemicals (stock) "TLP10F-1", etc.

The component (D) may contain, for example, surface-treated particles. Examples of the surface treatment include surface treatment with a surface treatment agent. The surface treatment agent is not particularly limited, and may include a surfactant such as a nonionic surfactant, an amphoteric surfactant, a cationic surfactant, an anionic surfactant, an inorganic fine particle, and the like. When the component (D) is a particle containing a fluororesin, a fluorine-based surfactant or the like is preferred from the viewpoint of affinity. Specific examples of the fluorine-based surfactants include "SurflonS-243" (perfluoroalkyl ethylene oxide adduct) manufactured by AGC Kiyomi Chemicals Corporation, "Megafac F-251" manufactured by DIC Corporation, and DIC (Megafac F-477), DIC (Megafac F-553), DIC (Megafac R-40), DIC (Megafac R-43), DIC (shares) "Megafac R-94", "FTX-218" by Neos, "Ftergent 610FM" by Neos, "Ftergent 730LM" by Neos, etc.

The content of the (D) component is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of reducing the dielectric constant of the insulating layer. It is preferably 15% by mass or more. The upper limit of the content of the component (D) is not particularly limited, but is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less. Therefore, the content of the (D) component is preferably 5 mass% to 40 mass%, more preferably 10 mass% to 35 mass% or more, and still more preferably 15 mass% to 30 mass%.

<(E) inorganic filler>

The resin composition of the present invention may further contain (E) an inorganic filler.

(E) The material of the component (inorganic filler) is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, glass, ochrerite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, Hydrotalcite, gibbsite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, Magnesium titanate, bismuth titanate, titanium oxide, zirconia, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate and the like. Among these, particularly preferred are silicon dioxide and aluminum oxide. The silicon dioxide is preferably spherical silicon dioxide. The inorganic fillers may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is not particularly limited. From the viewpoint of obtaining an insulating layer with a small surface roughness or from the viewpoint of improving the formation of fine wiring, it is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.1 μm or more, and still more preferably 0.3 μm or more. Have this Examples of commercially available inorganic fillers with an average particle diameter include, for example, "YC100C", "YA050C", "YA050C-MJE", "YA010C", manufactured by Admatechs, and "UFP-30" manufactured by Electrochemical Industries, Ltd. , (Stock) Tokuyama made "SilFile NSS-3N", "SilFile NSS-4N", "SilFile NSS-5N", (stock) Admatechs made "SC2500SQ", "SO-C4", "SO-C2", " SO-C1 "and so on.

The average particle size of the inorganic filler can be determined by laser diffraction based on Mie scattering theory. Scattering method to measure. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median particle diameter is used as the average particle diameter to measure. The measurement sample is preferably one in which an inorganic filler is dispersed in water by ultrasonic waves. The laser diffraction scattering type particle size distribution measuring device can use "LA-500" manufactured by Horiba Ltd.

The inorganic filler is preferably surface-treated with a surface-treating agent. Examples of the surface treatment agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, an alkoxysilane compound, an organic silazane compound, and a titanate-based coupling agent. These can be used individually by 1 type or in combination of 2 or more types. Commercial products of such surface treatment agents include, for example, "KBM-403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and "KBM" manufactured by Shin-Etsu Chemical Industry Co., Ltd. -803 "(3-mercaptopropyltrimethoxysilane)," KBE-903 "(3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Industry Co., Ltd., and" KBM "manufactured by Shin-Etsu Chemical Industry Co., Ltd. -573 "(N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd." SZ-31 "(Six (Methyl disilazane), Shin-Etsu Chemical Industry Co., Ltd. "KBM-103" (phenyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "KBM-4803" (long-chain epoxy-based silane coupling) Mixture), (C) component (fluorine contains silane compound), and the like.

The degree of surface treatment by the surface treatment agent is evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon content per unit surface area of the inorganic filler is preferably 0.05 mg / m ² or more, more preferably 0.1 mg / m ² or more, and still more preferably 0.2 mg / m from the viewpoint of improving the dispersibility of the inorganic filler. ² or more. In addition, from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the melt viscosity in the form of a sheet, it is preferably 1 mg / m ² or less, more preferably 0.8 mg / m ² or less, and still more preferably 0.5 mg / m ² or less. . The amount of carbon per unit surface area of the inorganic filler can be measured according to the method described in "Calculation of the amount of carbon per unit surface area" described later.

The content of the inorganic filler in the resin composition is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and more preferably 15 from the viewpoint of obtaining an insulating layer having a low thermal expansion coefficient. Mass% ~ 40 mass%. When the component (E) is surface-treated with the component (C), the content of the inorganic filler includes the content of the component (C).

The total content of the (D) component and the (E) component in the resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of obtaining an insulating layer having a lower dielectric constant and thermal expansion coefficient. It is more preferably 60% by mass or more.

<(F) thermoplastic resin>

The resin composition of the present invention may further contain (F) a thermoplastic resin.

Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyimide resin, polyetherimide resin, Polyfluorene resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, and preferably phenoxy resin. The thermoplastic resin can be used alone or in combination of two or more.

The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and even more preferably in the range of 20,000 to 60,000. The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight in terms of polystyrene of the thermoplastic resin can be measured using Shimadzu LC-9A / RID-6A, which is a measuring device, and Shodex K- manufactured by Showa Denko Corporation, which is a string. 800P / K-804L / K-804L, using chloroform or the like as a mobile phase, measured at a column temperature of 40 ° C, and calculated using a standard polystyrene calibration curve.

Examples of the phenoxy resin include those selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, One or more types of phenoxy resins composed of a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The end of the phenoxy resin can be any of the functions of phenolic hydroxyl, epoxy, etc. base. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resin containing a bisphenol A skeleton) and "YX8100BH30" (benzene containing a bisphenol S skeleton) made by Mitsubishi Chemical Corporation. Oxyresin), and "YX6954BH30" (phenoxy resin containing bisphenol acetophenone skeleton), others include "FX280" and "FX293" made by Nippon Steel & Sumikin Chemical Co., Ltd., and Mitsubishi Chemical Co., Ltd. "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794BH30", "YL7213BH30", "YL7290BH30", "YL7482BH30", etc.

Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include, for example, "electrochemical butyraldehyde 4000-2", "electrochemical butyraldehyde 5000-A", "electrochemical butyraldehyde 6000-C", " "Electrochemical butyraldehyde 6000-EP", S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" made by Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide (LINEAR POLYIMIDE) obtained by the reaction of a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a quaternary acid anhydride (Japanese Patent Laid-Open No. 2006-37083 Documented polyimide), polyimide containing a polysiloxane skeleton (Japan The modified polyimide described in Japanese Unexamined Patent Publication No. 2002-12667 and Japanese Unexamined Patent Publication No. 2000-319386 and the like.

Specific examples of the polyamidoimide resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Corporation. Specific examples of the polyimide resin include modified polymers such as "KS9100" and "KS9300" (polysiloxane imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Industries, Ltd. Amine amine imine.

Specific examples of the polyether fluorene resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

Specific examples of the polymer resin include polymer "P1700" and "P3500" made by Solvay Advanced Polymers.

Among them, the thermoplastic resin is preferably a phenoxy resin or a polyvinyl acetal resin. Therefore, in a more suitable embodiment, the thermoplastic resin includes one or more members selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% to 15% by mass, more preferably 0.6% to 12% by mass, and still more preferably 0.7% to 10% by mass.

<(G) Hardening accelerator>

The resin composition of the present invention may further contain (G) a hardening accelerator.

Examples of the hardening accelerator include a phosphorus-based hardening accelerator, an amine-based hardening accelerator, an imidazole-based hardening accelerator, a guanidine-based hardening accelerator, a metal-based hardening accelerator, and an organic peroxide-based hardening accelerator. Phosphorus-based hardening accelerator, amine-based hardening accelerator, imidazole-based hardening accelerator, and metal-based hardening accelerator, more preferably amine-based hardening accelerator, imidazole-based hardening accelerator, and metal-based hardening accelerator. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, osmium borate chloride compound, tetraphenyl osmium tetraphenyl borate, n-butyl osmium tetraphenyl borate, tetrabutyl osmium decanoate, (4- (Methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium Decanoate.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-ginsane (dimethyl Aminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo ( 5,4,0) -undecene.

Examples of the imidazole-based hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl- 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-benzene Imidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino- 6- [2'-undecylimidazolyl- (1 ')]-ethyl-s-tri Azine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isotricyanic acid adduct, 2-phenylimidazole isotricyanic 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 the like, and adducts of imidazole compounds and epoxy resins, Preferred are 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

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

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

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

Examples of the organic peroxide-based hardening accelerator include dicumyl peroxide, cyclohexanone peroxide, tert-butylperoxybenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide. Oxides, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydrogen peroxide, cumene hydroperoxide, tert-butylhydroperoxide Wait. As the organic peroxide-based hardening accelerator, a commercially available product can be used, and examples thereof include "Percumyl D" manufactured by Nippon Oil Corporation.

The content of the hardening accelerator in the resin composition is not particularly limited. When the nonvolatile content of the epoxy resin and the hardener is 100% by mass, it is preferably 0.01% by mass to 5% by mass.

<(H) flame retardant>

The resin composition of the present invention may further contain (H) a flame retardant. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, and a metal hydroxide. The flame retardant can be used alone or in combination of two or more.

Commercially available flame retardants can also be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., and "PX-200" manufactured by Daha Chemical Industry Co., Ltd., and the like.

When the resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably 0.5% by mass to 10%. quality%.

<(I) Other fillers>

The resin composition may contain (I) other fillers other than (D) component and (E) component from the viewpoint of improving elongation. (I) Any other filler can be used as the filler for forming an insulating layer of a printed circuit board, and examples thereof include rubber particles, polyamide fine particles, and silica particles.

Commercially available rubber particles can also be used, and examples thereof include "EXL2655" manufactured by Dow Chemical Japan Ltd. and "AC3816N" manufactured by Aica Industrial Co., Ltd.

When the resin composition contains the (I) component, the content is preferably 0.1% to 20% by mass, more preferably 0.2% to 10% by mass, and even more preferably 0.3% to 5% by mass, or 0.5%. Mass% ~ 3mass%.

<(J) any additive>

The resin composition may further contain other additives as necessary. Examples of the other additives include organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, and thickeners, defoamers, flatteners, and densers. Resin additives such as color imparting agents and coloring agents.

Further, the resin composition may further contain a polybutadiene structure and a urethane from the viewpoint of manufacturing a flexible printed circuit board. Structure, fluorene imine structure, and polyfluorene imine resin having a phenol structure at the molecular end. For details of the polyimide, refer to the description of International Publication No. 2008/153208, which is incorporated into the present specification.

The resin composition of the present invention can also bring a cured product having a lower specific dielectric constant. The specific permittivity of the cured product obtained by curing the resin composition of the present invention at a measurement frequency of 5.8 GHz is preferably 3.0 or less, more preferably 2.98 or less, and even more preferably 2.96 or less. The lower limit of the specific permittivity is not particularly limited, but may generally be 2.0 or more, 2.2 or more. In this way, the resin composition of the present invention can bring about a hardened product having a lower specific dielectric constant, and thus can significantly contribute to the thinning of the insulating layer. The specific permittivity of the hardened material can be measured according to the method described in "1. Measurement of specific permittivity" described later.

The resin composition of the present invention can also bring a cured product with a low thermal expansion coefficient. The average linear thermal expansion coefficient of the cured product obtained by curing the resin composition of the present invention from 25 ° C to 150 ° C is preferably 55 ppm / ° C or lower, more preferably 50 ppm / ° C or lower, and even more preferably 48 ppm / ° C or lower. , 46 ppm / ° C or lower, or 45 ppm / ° C or lower. The lower limit of the average linear thermal expansion coefficient is not particularly limited, and may generally be 10 ppm / ° C or higher, 15 ppm / ° C or higher, and the like. The average linear thermal expansion coefficient of the hardened material can be measured according to the method described in "2. Evaluation of the average linear thermal expansion coefficient" described later.

The resin composition of the present invention is suitably used as a resin composition for forming an insulating layer of a printed circuit board (resin composition for forming an insulating layer of a printed circuit board). Among them, when a printed circuit board is manufactured by a build-up method, it is suitable as a resin composition for forming an insulating layer (a resin composition for a build-up insulating layer of a printed circuit board). By using the tree of the invention The grease composition forms the insulating layer of the printed circuit board, and can realize a thin insulating layer having a low specific permittivity and excellent adhesion to the conductor layer.

[Laminated material]

The resin composition of the present invention can also be applied by application in a varnish state, but it is generally preferred to use it in the form of a sheet-like laminated material containing the resin composition in industry.

The sheet-like laminated material of the present invention contains the resin composition of the present invention. In the present invention, the sheet-like laminated material is preferably a resin sheet or a prepreg shown below.

In one embodiment, the resin sheet includes a support and a resin composition layer bonded to the support, and the resin composition layer is formed by the resin composition of the present invention.

The thickness of the resin composition layer is preferably 30 μm or less, more preferably 25 μm or less, and still more preferably 20 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and may generally be 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and preferably a film made of a plastic material and a metal foil.

When the support uses a thin film made of a plastic material, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate (hereinafter sometimes referred to as "PET") "PEN") and other polyester, polycarbonate (hereinafter sometimes referred to as "PEN") "PC"), acrylic acid such as polymethylmethacrylate (PMMA), cyclic polyolefins, triethyl cellulose (TAC), polyether sulfide (PES), polyetherketone, polyimide, etc. . Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and cheap polyethylene terephthalate is particularly preferred.

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

The support may be subjected to a matte treatment or a corona treatment to the surface bonded to the resin composition layer.

As the support, a support with a release layer having a release layer on a surface bonded to the resin composition layer can be used. The release agent used for the release layer of the support body with a release layer includes, for example, one or more members selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. Release agent. A commercially available product can be used as the support with a release layer, and examples thereof include PET films having a release layer containing an alkyd resin-based release agent as a main component, that is, "SK-1", "SK-1" made by Lintec "AL-5", "AL-7", Toray Co., Ltd. "LumirrorT6AM", etc.

Although the thickness of the support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

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

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol. Acetic esters such as acetate, cellosolve and carbitol such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide ( DMAc) and amine solvents such as N-methylpyrrolidone and the like. The organic solvents may be used singly or in combination of two or more kinds.

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

In the resin sheet, a protective film according to the support may be further laminated on a surface that is not bonded to the support of the resin composition layer (that is, a surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust or the like from adhering to or scratching the surface of the resin composition layer. The resin sheet can be rolled into a roll and stored. When the resin sheet has a protective film, it can be used by peeling off the protective film.

In one embodiment, the prepreg is applied to a sheet-like fiber substrate. It is formed by impregnating the resin composition of the present invention.

The sheet-like fibrous substrate used for the prepreg is not particularly limited, and those commonly used as a substrate for prepregs such as glass cloth, aromatic polyamide nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. From the viewpoint of reducing the thickness of the printed circuit board, the thickness of the sheet-like fiber substrate is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and still more preferably 600 μm or less. In particular, since the present invention can reduce the plating penetration depth, it is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 10 μm or less. The lower limit of the thickness of the sheet-like fibrous substrate is not particularly limited, and may generally be 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

The prepreg can be produced by a known method such as a hot melt method and a solvent method.

The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet.

The minimum melt viscosity of the resin composition layer (in the case of a prepreg, the resin composition impregnated in the sheet-like fibrous substrate) in the sheet-like laminated material is preferably 12000 poise from the viewpoint of obtaining good circuit embedding properties. (1200Pa.s) or less, more preferably 10000poise (1000Pa.s) or less, and more preferably 8000poise (800Pa.s) or less, 5000poise (500Pa.s) or less, or 4000poise (400Pa.s) or less. The lower limit of the minimum melt viscosity is preferably 100 poise (10 Pa.s) or more, more preferably 200 poise (20 Pa.s) or more, and more preferably 250 poise (from the viewpoint of maintaining a stable thickness even if the resin composition layer is thin. 25Pa.s) or more.

The minimum melt viscosity of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the melt viscosity decreases with an increase in temperature in the initial stage, and then, when it exceeds a certain level, the melt viscosity rises with the temperature increase. The lowest melt viscosity refers to the melt viscosity of this minimum point. The minimum melt viscosity of the resin composition layer can be measured using a dynamic viscoelasticity method, for example, it can be measured according to the method described in 3. Measurement of the minimum melt viscosity of the resin composition layer described later.

〔A printed circuit board〕

The printed circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention.

The printed circuit board of the present invention can be produced, for example, by using the above-mentioned resin sheet and a method including the following steps (I) and (II).

(I) bonding the resin composition layer of the resin sheet to the inner layer substrate on the inner layer substrate to perform the step of laminating the resin sheet, (II) A step of thermally curing the resin composition layer to form an insulating layer.

The "inner substrate" used in step (I) mainly refers to the main glass epoxy substrate, metal substrate, ceramic substrate, polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene ether substrate. A substrate, a PTFE substrate, an LCP (liquid crystal polymer) substrate, or a circuit substrate on which one or both sides of the substrate is formed with a patterned conductive layer (circuit). In addition, when manufacturing a printed circuit board, an insulating layer and / or a conductor should be formed. The inner-layer circuit substrate of the intermediate product of the layers is also included in the "inner-layer substrate" of the present invention. When the printed circuit board is a component-embedded circuit board, an inner-layer substrate (conductor layer is also referred to as a wiring layer) may be used.

The lamination of the inner substrate and the resin sheet can be performed, for example, by heating and pressure-bonding the resin sheet to the inner substrate from the side of the support. A member (hereinafter, also referred to as a “heat-compression-bonding member”) that heat-compresses a resin sheet to an inner layer substrate includes, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of pressing the heat and pressure bonding member directly on the resin sheet, it is preferable to press the resin sheet to sufficiently follow the unevenness of the surface of the inner substrate via an elastic material such as heat-resistant rubber.

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

Lamination can be performed by a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Nagaku Seisakusho, and a vacuum coater manufactured by Nichigo-Morton.

After lamination, the resin sheet after lamination can also be smoothed by pressing under pressure (atmospheric pressure), for example, by pressing the heat-pressing member from the support side. The smoothing conditions can be The conditions of the thermocompression bonding of the above-mentioned lamination are the same. The smoothing treatment can be performed by a commercially available laminator. The lamination and smoothing treatment can also be performed continuously using the commercially available vacuum laminator.

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

In step (II), the resin composition layer is thermally cured to form an insulating layer.

The conditions for the thermosetting of the resin composition layer are not particularly limited, and conditions generally used when forming an insulating layer of a printed wiring board can be used.

For example, the thermal curing conditions of the resin composition layer also vary depending on the type of the resin composition, but the curing temperature may be in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably 170). ℃ ~ 200 ℃), the hardening time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

Before the resin composition layer is thermally hardened, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, before the resin composition layer is thermally cured, the resin composition layer may be prepared at a temperature of 50 ° C or higher and less than 120 ° C (preferably 60 ° C or higher and 110 ° C or lower, more preferably 70 ° C or higher and 100 ° C or lower). Heating for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

When manufacturing a printed circuit board, (III) a step of making holes in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be performed in accordance with the technical field used in the manufacture of printed circuit boards. It is usually carried out by various methods known to a person skilled in the art. In addition, when the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or step (IV). And step (V).

Step (III) is a step of making a hole in the insulating layer, so that a via hole, a through hole, etc. can be formed in the insulating layer. Step (III) can be performed according to the composition of the resin composition used for forming the insulating layer, for example, using a drill, a laser, a plasma, or the like. The size or shape of the hole can be appropriately determined according to the design of the printed circuit board.

Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and a known order and conditions generally used when forming an insulating layer of a printed circuit board can be adopted. For example, a swelling treatment using a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution may be sequentially performed to roughen the insulating layer. The swelling liquid is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred, and the alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Commercially available swelling liquids include, for example, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atoteeh Japan. The swelling treatment by the swelling liquid is not particularly limited. For example, it can be performed by immersing the insulating layer in a swelling liquid at 30 ° C to 90 ° C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to a moderate level, it is preferred that the hardened body is immersed in a swelling liquid at 40 ° C to 80 ° C for 5 minutes to 15 minutes. The oxidant (roughened solution) is not particularly limited, and examples thereof include potassium permanganate dissolved in an aqueous solution of sodium hydroxide or Alkaline permanganate solution of sodium permanganate. The roughening treatment of an oxidant such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidant solution heated to 60 ° C to 80 ° C for 10 minutes to 30 minutes. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Examples of commercially available oxidants include alkaline permanganic acid solutions such as "Concentrate Compact CP", "Concentrate Compact P", and "Dosing Solution Securiganth P" manufactured by Atotech Japan. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction solution Securiganth P" manufactured by Atotech Japan. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened with an oxidizing agent in a neutralizing solution at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralization solution at 40 ° C to 70 ° C for 5 to 20 minutes is preferred.

Step (V) is a step of forming a conductor layer.

The conductive material used for the conductive layer is not particularly limited. In a more suitable embodiment, the conductor layer contains one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. . The conductor layer may be a single metal layer or an alloy layer. Examples of the alloy layer include an alloy (for example, nickel, chromium alloy, copper, nickel alloy, and copper-titanium alloy) selected from the group consisting of two or more metals. Of layers. Among them, from the viewpoints of versatility, cost, and ease of patterning of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper is preferred; or nickel. Chrome alloy, copper. Nickel alloy, copper. Titanium alloy A gold layer, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel. An alloy layer of a chromium alloy, and more preferably a single metal layer of copper.

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

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

In one embodiment, the conductive layer can be formed by plating. For example, a conventionally known technique such as a semi-additive method and a full-additive method can be used to plate the surface of the insulating layer to form a conductive layer having a desired wiring pattern. An example of forming a conductive layer by a semi-additive method is shown below.

First, a shield layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating protection layer, a mask pattern corresponding to a desired wiring pattern and exposing a part of the plating protection layer is formed. On the exposed plating protection layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, an unnecessary plating protection layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

When using a resin sheet with a metal foil as a support, a conductor layer can be formed by a subtractive process or a semi-additive method using a metal foil derived from a resin sheet.

The resin composition of the present invention can be used even when the printed circuit board is a built-in circuit board. Built-in circuit board for parts Manufactured by conventional methods.

In other embodiments, the printed circuit board of the present invention can be manufactured using the above-mentioned prepreg. The manufacturing method is basically the same as when a resin sheet is used.

The surface roughness of the insulating layer formed by the hardened product of the resin composition of the present invention after the roughening treatment is low. Specifically, the arithmetic average roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment indicate good results. The arithmetic average roughness (Ra) is preferably 500 nm or less, more preferably 450 nm or less, and still more preferably 400 nm or less. The lower limit is not particularly limited, and may be 100 nm or more. The root mean square roughness (Rq) of the surface of the insulating layer is preferably 600 nm or less, more preferably 550 nm or less, and even more preferably 530 nm or less. The lower limit is not particularly limited, and may be 100 nm or more. The evaluation of the arithmetic mean roughness (Ra) and the root mean square roughness (Rq) can be measured according to a method described below (measurement of arithmetic mean roughness (Ra) and root mean square roughness (Rq)).

The printed circuit board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. Therefore, the adhesion (peel strength) of the insulating layer and the conductor layer after the roughening treatment indicates good results. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.4 kgf / cm or more, It is more preferably 0.45 kgf / cm or more. The upper limit is not particularly limited, and may be 1.2 kgf / cm or less, 0.9 kgf / cm or less, etc. In the present invention, the arithmetic average roughness (Ra) and uniformity of the insulating layer even after roughening treatment Low square root roughness (Rq) can also form a guide with such high peel strength Body layer, so it is obviously helpful for fine wiring of printed circuit boards. Evaluation of peeling strength can be measured according to the method described in (Measurement of peeling strength) mentioned later.

[Fingerprint authentication sensor]

The fingerprint authentication sensor 1 of the present invention is characterized by including an insulating layer 3 formed of a cured product of the resin composition of the present invention. Hereinafter, the fingerprint authentication sensor 1 will be described with reference to FIG. 1.

As shown in FIG. 1, the fingerprint authentication sensor 1 is provided with a metal electrode 5 on the surface of the printed circuit board 2 through an insulating layer 3 formed by the hardened material of the resin composition of the present invention, and the insulating layer 4 covers the insulating layer. The constituent of the surface on the side of the metal electrode 3 of 3.

In the fingerprint authentication sensor 1 of the present invention, the insulating layer 3 can be formed by the same method as the insulating layer of the printed circuit board described above.

The fingerprint authentication sensor 1 directly places a finger (not shown) on the insulating film 4 and detects the unevenness of the fingerprint. The capacitor is formed by the fingers of the conductor, the metal electrode 5, and the insulating film 4. Since the distance between the concave portion and the convex portion of the fingerprint to the metal electrode 5 is different, the difference in the distance becomes the difference in the capacitance value of the formed capacitor. Here, the convex part of the fingerprint determines the capacity value due to the specific permittivity of the insulating coating 4, but the concave part of the fingerprint has an air layer to enter, so the capacity value of the convex part and the concave part changes greatly due to the difference in distance.

The fingerprint authentication sensor 1 uses a known principle as described above and includes a specific permittivity obtained by curing the resin composition of the present invention. The insulating layer 3 can be reduced in thickness and can be miniaturized.

[Semiconductor device]

The semiconductor device of the present invention includes the printed circuit board of the present invention or the fingerprint authentication sensor of the present invention.

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

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor wafer) due to a conductive portion of a printed circuit board. "Continuity" means "a place where electrical signals are transmitted on a printed circuit board". The place may be a surface or an embedded place. The semiconductor wafer is not particularly limited as long as it is an electric circuit element using a semiconductor as a material.

The method for mounting a semiconductor wafer when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor wafer can effectively function, and specifically, a wire bonding mounting method, a flip chip mounting method, A mounting method for a bumpless layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method by bumpless layer (BBUL)" refers to the "mounting method of directly embedding a semiconductor wafer in a recessed portion of a printed circuit board and connecting the semiconductor wafer to the wiring on the printed circuit board." .

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. In addition, in the following description, "part" and "%" show "mass part" and "mass%" respectively unless otherwise stated.

[Example 1]

20 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 187, "jER828US" manufactured by Mitsubishi Chemical Corporation), bisxylenol type epoxy resin (epoxy equivalent 190, manufactured by Mitsubishi Chemical Corporation) YX4000HK '') 10 parts, biphenylaralkyl-based epoxy resin (epoxy equivalent 276, Nippon Kayaku Co., Ltd. `` NC3000 '') 30 parts, naphthol-type epoxy resin (epoxy equivalent 332, Nissin 10 parts of "ESN475V" manufactured by Tetsujukin Chemical Co., Ltd., and 20 parts of "YX7553BH30" manufactured by Mitsubishi Chemical Co., Ltd. and phenoxy resin (30% solids MEK / cyclohexanone = 1/1 solution) Heat and dissolve in 60 parts of MEK and 20 parts of cyclohexanone while stirring. Mix active ester hardener (active group equivalent 223, 65% by mass of non-volatile content in toluene solution, "HPC8000-65T" made by DIC Corporation ) 15 parts, cresol novolac type hardener containing a triazine skeleton (151 phenol equivalents, 2-methoxypropanol solution with 50% solids content, "LA3018-50P" manufactured by DIC Corporation), hardening Accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass%) 4 parts, 3,3,3-trifluoropropyltrimethoxysilane (made by Shin-Etsu Chemical Industry Co., Ltd., "KBM-7103") 4 copies, Spherical silicon dioxide N- phenyl-3-aminopropyl trimethoxy Silane (by Shin-Etsu Chemical (shares) manufactured by "KBM573") surface-treated (Admatechs (shares) manufactured by "SO-C2", average particle diameter 0.5 μm) 100 parts, PTFE particles ("ruburon L-2" manufactured by Daikin Industries, Inc., average particle size 3 μm, specific permittivity 2.0-2.2 at measurement frequency 5.8 GHz) 80 parts, uniformly dispersed using a high-speed rotary mixer , Making resin varnish. Next, a polyethylene terephthalate film (thickness: 38 μm, manufactured by Lintec, Inc., “AL5”) with an alkyd resin-based release layer as a support was prepared. The prepared resin varnish was uniformly coated on the support with a die coating machine, and dried at 80 to 120 ° C (average 100 ° C) for 6 minutes to form a resin composition layer. The thickness of the resin composition layer was 50 μm, and the amount of residual solvent in the resin composition was about 2% by mass. Next, a 15 μm-thick polypropylene film was laminated on the surface of the resin composition layer and rolled into a roll shape. The roll-shaped resin sheet was thinly cut into a width of 507 mm, thereby obtaining a sheet-like resin sheet having a size of 507 mm × 336 mm.

[Example 2]

In addition to replacing 80 parts of PTFE particles ("ruburonL-2" manufactured by Daikin Industries, with an average particle diameter of 3 μm), a fluorine-based surfactant (perfluoroalkyl ethylene oxide adduct, AGC Kiyomi) was used in advance. Except for 84 parts obtained from 4 parts of "SurflonS-243" manufactured by Chemical Co., Ltd. and 80 parts of PTFE particles ("ruburonL-2" manufactured by Daikin Industries, Inc., with an average particle size of 3 μm), the same process as in Example 1 Resin varnish to obtain resin flakes.

[Example 3]

In addition to replacing 30 parts of biphenylaralkyl type epoxy resin (epoxy equivalent 276, "NC3000" manufactured by Nippon Kayaku Co., Ltd.), a naphthalene ether type epoxy resin (epoxy equivalent 250, DIC (share) Except for 27 parts of "HP6000"), a resin varnish was produced in the same manner as in Example 1 to obtain a resin sheet.

[Example 4]

In addition to replacing 15 parts of active ester hardener (active group equivalent 223, toluene solution with 65% by mass of non-volatile content, "HPC8000-65T" manufactured by DIC Corporation, and a cresol novolac type hardener containing a triazine skeleton ( Phenol equivalent 151, 50% 2-methoxypropanol solution, 25 parts of "LA3018-50P" manufactured by DIC (stock), and naphthalene hardener (phenol equivalent 215, Nippon Steel & Sumikin Chemical Co., Ltd.) Except for 15 parts of "SN485") and 12 parts of a phenol novolac type hardener containing a triazine skeleton (125 phenol equivalent, 60% solids MEK solution, "LA7054" made by DIC), and Example 1 A resin varnish was produced in the same manner to obtain a resin sheet.

[Example 5]

In addition to the varnish produced in Example 1, 2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the resin was uniformly dispersed in a high-speed rotary mixer to prepare a resin. Except for the varnish, a resin varnish was produced in the same manner as in Example 1 to obtain a resin sheet.

[Comparative Example 1]

A resin varnish was produced in the same manner as in Example 1 except that 4 parts of 3,3,3-trifluoropropyltrimethoxysilane ("KBM-7103" manufactured by Shin-Etsu Chemical Co., Ltd.) was not used, and a resin sheet was obtained.

[Comparative Example 2]

In addition to replacing the surface-treated spherical silica (N-phenyl-3-aminopropyltrimethoxysilane) (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.) (SO-C2 manufactured by admatechs Corporation) , 100 parts with an average particle diameter of 0.5 μm) and 80 parts with PTFE particles (“ruburonL-2” manufactured by Daikin Industries, Inc., with an average particle diameter of 3 μm), and N-phenyl-3-aminopropyltrimethoxy The same as in Comparative Example 1 except for 180 parts of base silicon silane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) and surface-treated spherical silicon dioxide ("SO-C2" manufactured by admatechs (stock), average particle diameter: 0.5 μm) A resin varnish was produced to obtain a resin sheet.

[Comparative Example 3]

In addition to N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), a spherical silica ("SO-C2" manufactured by admatechs) (Average particle size: 0.5 μm) except that the blending amount was changed to 80 parts, and a resin varnish was produced in the same manner as in Comparative Example 1 to obtain a resin sheet.

[Comparative Example 4]

In addition to the varnish produced in Comparative Example 1, a fluorine-based interfacial activity was added. After 4 parts of an agent ("SurflonS-243" manufactured by AGC Kiyomi Chemical Co., Ltd.), a resin varnish was produced in the same manner as in Comparative Example 1 except that the resin varnish was uniformly dispersed using a high-speed rotary mixer to obtain a resin sheet.

[Comparative Example 5]

In addition to the varnish produced in Comparative Example 1, 2 parts of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the resin was uniformly dispersed in a high-speed rotary mixer to prepare a resin. Except for the varnish, a resin varnish was produced in the same manner as in Comparative Example 1 to obtain a resin sheet.

<Measurement method. Evaluation method>

Explain various measurement methods. Evaluation method.

1. Measurement of specific permittivity

The resin varnishes obtained in the examples and comparative examples were uniformly coated on a PET film ("Lintec (KK)", "PET501010")) subjected to mold release treatment with a die coater, and the resin composition layer after drying was applied. The thickness was 50 μm, and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed at 200 degreeC for 90 minutes, and peeled from the support body, and obtained the hardened | cured material film. This hardened film was cut to have a length of 80 mm and a width of 2 mm as evaluation samples. For this evaluation sample, an HP8362B device manufactured by Agilent Technologies was used, and the specific permittivity was measured by a Cavity Perturbation Method at a measurement frequency of 5.8 GHz and a measurement temperature of 23 ° C. Enter 2 test pieces Take measurements and calculate the average value, as shown in Table 1.

2. Evaluation of average linear thermal expansion coefficient>

The resin varnishes obtained in the examples and comparative examples were uniformly coated on a PET film ("Lintec (KK)", "PET501010")) subjected to mold release treatment with a die coater, and the dried resin composition layer The thickness was 50 μm, and dried at 80 to 110 ° C. (average 95 ° C.) for 6 minutes. Then, it heat-processed at 200 degreeC for 90 minutes, and peeled from the support body, and obtained the hardened | cured material film. This hardened film was cut into test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile weighting method using a Rigaku thermomechanical analysis device (Thermo Plus TMA8310). After the test piece was installed in the aforementioned device, the measurement was performed continuously twice under measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C./minute. In the second measurement, the average linear thermal expansion coefficient from 25 ° C to 150 ° C was calculated and shown in Table 1.

3. Measurement of minimum melt viscosity of resin composition layer

The minimum melt viscosity of the resin composition layer in the resin sheets produced in the examples and comparative examples was measured. A dynamic viscoelasticity measuring device (Rheosol-G3000 made by UBM) was used. The amount of resin was 1 g. A parallel plate with a diameter of 18 mm was used. The starting temperature was 60 ° C to 200 ° C, and the temperature was increased by 5 ° C / min. The temperature interval was 2.5. Measure the lowest melting viscosity under the conditions of ℃ and vibration of 1Hz / deg, as shown in Table 1.

4. Evaluation of dispersibility of resin varnish

The aggregates in the resin varnishes obtained in the examples and comparative examples were observed using a microscope (VH-2250, manufactured by KEYENCE) at an observation magnification of 1000 times. When there are 0 or more aggregates of 50 μm or more in 3 fields of view, and less than 6 of aggregates of 40 μm or more in 3 fields of view, it is indicated by ○, and one or more aggregates of 50 or more μm in 3 fields of view, or 40 μm The above-mentioned aggregates are 6 or more, and are represented by ×. The results are shown in Table 1.

5. Measurement of the adhesion (peel strength) of the plated conductor layer by the semi-additive method (1) Bottom layer processing of inner circuit board

Both sides of the glass cloth substrate epoxy resin on which the inner layer circuit was formed were bonded to a copper laminate (18 μm in thickness of copper foil, 0.8 mm in thickness of the substrate, and R5715ES manufactured by Matsushita Electric Works Co., Ltd.) using CZ8100 manufactured by Mec Corporation. 1 μm for roughening the copper surface.

(2) Laminating the film

The resin sheets prepared in the examples and comparative examples were subjected to a batch vacuum press laminator (two-stage laminating machine CVP700 manufactured by nikko-materials) to contact the resin composition layer with the inner substrate and Bonded to both sides of the inner substrate. The lamination system was carried out by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then performing pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, it was hot-pressed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Hardening of resin composition

The laminated resin sheet was cured at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes to harden the resin composition to form an insulating layer. Then, the PET film was peeled.

(4) Roughening

The inner circuit board with the insulating layer formed was immersed in a swelling liquid: Swelling Dip Securiganth P containing diethylene glycol monobutyl ether at Atotech Japan (stock), and immersed at 60 ° C for 5 minutes, and then used as a roughening solution : Concentrate CompactP (KMnO ₄ : 60g / L, NaOH: 40g / L aqueous solution) of Atotech Japan (stock), immersed at 80 ° C for 10 minutes, and finally, as a neutralization solution: Atotech Japan (Stock) Reduction Solution Securiganth P was immersed at 40 ° C for 5 minutes.

(5) Plating by semi-additive method

In order to form a circuit on the surface of the insulating layer, the inner circuit board treated with (4) was immersed in an electroless plating solution containing PdCl ₂ at 40 ° C for 5 minutes, followed by an electroless copper plating solution at 25 ° C for 20 minutes. . After heating at 150 ° C. for 30 minutes, an annealing treatment was performed to form an etching resist. After patterning was performed by etching, copper sulfate plating was performed to form a conductor layer with a thickness of 25 μm. Next, annealing was performed at 180 ° C for 30 minutes. The obtained circuit board was used as an evaluation board A. For this evaluation board A, the tensile peel strength (peel strength) of the plated conductor layer was measured.

(6) Measurement of tensile peel strength (peel strength) of the plated conductor layer by the semi-additive method

On the conductor layer of the evaluation substrate A produced in (5), a cut of 10 mm wide and 100 mm in length was applied, and one end was peeled off, and it was clamped with a ((share) TSE, Autocom type testing machine AC-50CSL), At room temperature, a load (kgf / cm) at a speed of 50 mm / minute and 35 mm of peeling in the vertical direction was measured, as shown in Table 1.

6. Measurement of adhesion (peel strength) with metal foil conductor layer (1) Preparation of the inner substrate

On both sides of the glass cloth substrate epoxy resin on which the circuit is formed, a copper laminate (thickness of copper foil of 18 μm, substrate thickness of 0.8 mm, and “R1515A” manufactured by Matsushita Electric Works Co., Ltd.) was microetched (MEC (stock) ("CZ8100") was etched to 1 μm, and the copper surface was roughened.

(2) Lamination of copper foil with resin

The resin varnishes obtained in the examples and comparative examples were uniformly coated on a MT18Ex foil made by Mitsui Metals Industry Co., Ltd. with a die coater so that the thickness of the dried resin composition layer was 50 μm, and the temperature was 80 to 110 ° (Average 95 ° C.) was dried for 6 minutes to obtain a resin-coated copper foil (copper foil formed with a resin composition). This copper foil with resin was used in a batch type vacuum pressure laminator (two-stage laminating machine made by nikko-materials) CVP700), the resin composition layer is brought into contact with the inner substrate and laminated on both sides of the inner substrate. The lamination system was carried out by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then performing pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, it was hot-pressed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Hardening of copper foil with resin

The resin-coated copper foil after lamination was cured at 200 ° C. for 90 minutes to harden the resin composition to form a cured body (coated copper foil) with the copper foil.

(4) Plating

(3) From the obtained hardened body with copper foil, the carrier copper foil was peeled off, and then copper sulfate electrolytic copper plating was performed to a thickness of 25 μm to form a conductor layer. Next, annealing was performed at 180 ° C for 30 minutes. The obtained circuit board was used as an evaluation board B. For this evaluation board B, the tensile peel strength (peel strength) of the conductor layer was measured.

(5) Measurement of the adhesion (peel strength) of the conductor layer

On the conductor layer of the evaluation substrate B produced in (4), a cut of 10 mm in width and 100 mm in length was applied, and one end was peeled off, and it was held with a tool ((share) TSE, Autocom type testing machine AC-50CSL), room temperature During the test, the load (kgf / cm) at a speed of 50 mm / minute and 35 mm in the vertical direction was peeled off, as shown in Table 1.

Table 1 shows the above evaluation results and measurement results, and also reveals the materials used in the production of each resin varnish and their blending amounts (mass parts of non-volatile components) and (D) components and ( E) The total ratio (% by mass) of the components.

Claims (18)

A resin composition containing (A) an epoxy resin, (B) a hardener, (C) a fluorine atom-containing alkoxysilane compound, and (D) an organic filler. The resin composition of claim 1, wherein the average particle diameter of the component (D) is 0.05 μm to 5 μm. The resin composition according to claim 1, wherein the (D) component is particles having a specific dielectric constant of 2.8 or less at a measurement frequency of 5.8 GHz. The resin composition according to claim 1, wherein the component (D) is particles containing a fluororesin. The resin composition of claim 1, wherein the number of fluorine atoms in one molecule of the component (C) is 1 to 10. The resin composition of claim 1, wherein the number of alkoxy groups in one molecule of the component (C) is 1 to 5. The resin composition according to claim 1, wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane. The resin composition according to claim 1, further comprising (E) an inorganic filler. The resin composition of claim 8, wherein the total content of the (D) component and the (E) component is 50% by mass or more when the nonvolatile component in the resin composition is 100% by mass. The resin composition of claim 1, which has a specific dielectric constant of 3.0 or less at a measurement frequency of 5.8 GHz of a hardened material obtained by curing the resin composition, and an average linear thermal expansion coefficient from 25 ° C to 150 ° C of 55 ppm / ° C. the following. The resin composition of claim 1, which is used for forming an insulating layer of a printed circuit board. The resin composition of claim 1 is for a build-up insulating layer of a printed circuit board. A sheet-like laminated material comprising the resin composition according to any one of claims 1 to 12. A sheet-like laminated material comprising a resin composition layer formed of the resin composition according to any one of claims 1 to 12. The laminar laminate of claim 14, wherein the resin composition layer The thickness is 30 μm or less. A printed circuit board comprising an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 12. A fingerprint authentication sensor includes an insulating layer formed by a hardened product of the resin composition of any one of claims 1 to 12. A semiconductor device includes a printed circuit board of claim 16 or a fingerprint authentication sensor of claim 17.