JP2017119846A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that can reduce the roughness of an insulating layer surface and is excellent in peel strength between an insulating layer and a conductor layer after roughening as well as plating submersion depth, component embedding, and flame retardancy; a sheet-like laminate material comprising the resin composition, a printed wiring board comprising an insulating layer formed from a cured product of the resin composition, and a semiconductor device.SOLUTION: A resin composition comprises (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a sheet-like laminate material containing the resin composition, a printed wiring board including an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked on an inner substrate is known. The insulating layer is generally formed by curing a resin composition.

  For example, Patent Document 1 discloses a resin composition containing an inorganic filler surface-treated with an epoxy resin, a curing agent, and an alkoxysilane compound, and the average particle size of the inorganic filler is 0.01 μm to 5 μm. In addition, a resin composition in which the content of the inorganic filler is 30% by mass to 90% by mass when the nonvolatile component in the resin composition is 100% by mass is disclosed.

  Patent Document 2 discloses a resin composition containing an epoxy resin, a curing agent, and an inorganic filler, the inorganic filler being surface-treated with an aminoalkylsilane, and a nonvolatile component in the resin composition When the content is 100% by mass, a resin composition in which the content of the inorganic filler is 55% by mass to 90% by mass is disclosed.

JP 2014-12763 A JP 2014-28880 A

  2. Description of the Related Art In recent years, electronic devices have been reduced in size and performance, and in printed wiring boards, build-up layers have been multilayered, and fine wiring and high density have been desired. By using the resin compositions disclosed in Cited Document 1 and Cited Document 2, the arithmetic average roughness of the surface of the insulating layer can be lowered in the wet roughening step, and a conductor layer having sufficient peel strength can be formed. However, further improvement in performance is desired in terms of plating depth, component embedding property, flame retardancy, and the like.

  The object of the present invention is to reduce the roughness of the surface of the insulating layer, and to provide a resin composition having a good peel strength between the insulating layer and the conductor layer after the roughening treatment, a plating depth, a part embedding property, and a flame retardancy. An object of the present invention is to provide a sheet-like laminate material containing the resin composition, a printed wiring board including an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a fluorine atom-containing alkoxysilane compound, and have completed the present invention.

That is, the present invention includes the following contents.
[1] A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.
[2] The resin composition according to [1], wherein the content of the component (D) is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass.
[3] The resin composition according to [1] or [2], wherein the average particle diameter of the component (D) is 0.01 μm to 2 μm.
[4] The resin composition according to any one of [1] to [3], wherein the component (D) is silica or alumina.
[5] The resin composition according to any one of [1] to [4], wherein the number of fluorine atoms in one molecule of (C) component is 1 to 10.
[6] The resin composition according to any one of [1] to [5], wherein the number of alkoxy groups in one molecule of component (C) is 1 to 5.
[7] The resin composition according to any one of [1] to [6], wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane.
[8] The resin composition according to any one of [1] to [7], wherein the component (D) is surface-treated with the component (C).
[9] The resin composition according to any one of [1] to [8], which is for forming an insulating layer of a printed wiring board.
[10] The resin composition according to any one of [1] to [9], which is for a buildup layer of a printed wiring board.
[11] A sheet-like laminated material comprising the resin composition according to any one of [1] to [10].
[12] A sheet-shaped laminated material including a resin composition layer formed of the resin composition according to any one of [1] to [10].
[13] The sheet-shaped laminated material according to [12], wherein the resin composition layer has a thickness of 10 μm or less.
[14] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [10].
[15] A semiconductor device comprising the printed wiring board according to [14].

  According to the present invention, the roughness of the surface of the insulating layer can be lowered, and the resin composition has good peel strength between the insulating layer and the conductor layer after the roughening treatment, the plating penetration depth, the component embedding property, and the flame retardancy. A sheet-like laminate material containing the resin composition, a printed wiring board including an insulating layer formed of a cured product of the resin composition, and a semiconductor device can be provided.

FIG. 1 is a schematic view showing an example of a cross section of the component temporary bonding inner layer substrate.

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

[Resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.

  Hereinafter, each component contained in the resin composition of the present invention will be described in detail.

<(A) Epoxy resin>
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak 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, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type Epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring Epoxy resins, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (A) is preferably at least one selected from bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component 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, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation. Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, "Celoxide 2021P" manufactured by Daicel Corporation "(Fat having an ester skeleton) Type epoxy resin), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd., Mitsubishi Chemical Corporation “630LSD” (a glycidylamine type epoxy resin) manufactured by the same company may be used. These may be used alone or in combination of two or more.

  Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(Cresol novolac type epoxy resin)", "N-695" (Cresol novolac type epoxy resin), "HP-7200" (Dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA -7311 "," EXA-7311-G3 "," EXA-7311-G4 "," EXA-7311-G4S "," HP6000 "(naphthylene ether type epoxy resin)," EPPN "manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC7000L "(naphthol novolak type) Poxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak) Type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical “PG-100”, “CG-500” manufactured by Mitsubishi Chemical Corporation, “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), Mitsubishi Chemical Corporation “JER1010” (solid bisfer Lumpur A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as an epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1:15 in terms of mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 8 is even more preferable.

  The content of the epoxy resin in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. That's it. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less.

  In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.

  The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Curing agent>
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples thereof include carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (B) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent and a cyanate ester curing agent.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Co., Ltd. “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” and the like manufactured by DIC Corporation.

  From the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, an active ester curing agent is also preferable. Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally 1 molecule of ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are carried out. A compound having two or more thereof is preferably used. The active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound 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, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. 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 acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC Corporation)," EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and as an active ester compound containing an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and “DC808” as an active ester curing agent which is an acetylated product of phenol novolac. "( "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation) as active ester-based curing agents that are benzoylated phenol novolaks Chemical Co., Ltd.).

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. For example, a prepolymer partially or wholly converted into a trimer).

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.

  In one embodiment, the resin composition includes the aforementioned (A) epoxy resin and (B) a curing agent. The resin composition is a mixture of a liquid epoxy resin and a solid epoxy resin (A) as an epoxy resin (mass ratio of liquid epoxy resin: solid epoxy resin is preferably 1: 0.1 to 1:15, more preferably 1: 0.3-1: 10, more preferably 1: 0.6-1: 8) (B) phenolic curing agent, naphtholic curing agent, active ester curing agent and cyanate ester One or more selected from the group consisting of curing agents (preferably one or more selected from the group consisting of phenolic curing agents, naphthol curing agents and active ester curing agents) are preferably included.

  Although content of the hardening | curing agent in a resin composition is not specifically limited, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less. The lower limit is not particularly limited, but is preferably 0.5% by mass or more.

<(C) Fluorine atom-containing alkoxysilane compound>
The resin composition of this invention contains (C) component. As a result of intensive studies by the present inventors, by including the component (C), the roughness of the surface of the insulating layer can be reduced, and a conductor layer having sufficient peel strength can be formed, and the plating depth is also reduced. The present inventors have found that the component embedding property and flame retardancy are good. Component (C) is chemically stable. For this reason, the tolerance with respect to an oxidizing agent (desmear liquid) is high, roughness and plating depth can be lowered, and the peel strength can be improved accordingly. Moreover, since (C) component is flame-retardant, even if it does not contain the flame retardant mentioned later, a flame retardance can be provided.

  Component (C) is preferably 1 to 10 fluorine atoms and 1 to 1 fluorine atoms in the molecule of component (C) from the viewpoint of reducing the resistance to the oxidizing agent used for the roughening treatment and reducing the depth of plating. 5 is more preferable, and the number of fluorine atoms is more preferably 1 to 3.

The component (C) preferably has a fluorinated alkyl group from the viewpoint of reducing the resistance to the oxidizing agent used in the roughening treatment and reducing the depth of plating, and the fluorinated alkyl group preferably has a fluorine atom at the terminal. . The fluorinated alkyl group is preferably a fluorinated alkyl group having 1 to 20 carbon atoms, more preferably a fluorinated alkyl group having 1 to 10 carbon atoms, and further preferably a fluorinated alkyl group 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. Examples include CF ₃ , —CH ₂ CH (CF ₃ ) ₂ , —C (CF ₃ ) ₃ , and —CH ₂ CH ₂ CF ₃ is preferable.

  In addition, from the viewpoint of improving reactivity, the component (C) preferably has 1 to 5 alkoxy groups, more preferably 1 to 3 alkoxy groups in one molecule of the component (C), and the number of alkoxy groups. Is more preferably 2 to 3.

  The alkoxy group in 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 an alkoxy group having 1 to 6 carbon atoms from the viewpoint of improving reactivity. More preferred are groups. Examples of such alkoxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, s-butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, and heptyloxy. Group, octyloxy group, nonyloxy group, and decyloxy group, and methoxy group is preferable.

The alkoxy group may have a substituent. The substituent is not particularly limited, for example, a halogen atom, -OH, _{-O-C 1-6} alkyl group, -N _{(C 1-6 alkyl) 2, C 1-6 alkyl, C 6- A 10} aryl group, —NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like.

Here, the term “C _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

  The above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.

  The molecular weight of the component (C) is preferably 50 to 2000, more preferably 75 to 100, and still more preferably 100 to 500 from the viewpoint of improving compatibility.

  Among these, examples of the component (C) include 3,3,3-trifluoropropyltrimethoxysilane, perfluoro (poly) ether group-containing alkoxysilane compounds, and the like. These may be used alone or in combination of two or more. Among these, 3,3,3-trifluoropropyltrimethoxysilane is preferable as the component (C). (C) A commercial item may be used for a component, for example, Shin-Etsu Chemical Co., Ltd. product "KBM-7103", "OPTOOL DSX" etc. are mentioned.

Although the aspect of (C) component contained in the resin composition of this invention is not specifically limited, It is preferable to contain in the resin composition in the aspect of the following (i)-(iii), (i) or (iii) ) Is more preferably contained in the resin composition, and more preferably in the resin composition in the form (i). That is, the component (C) is preferably contained in the resin composition as a surface treatment agent for the component (D).
(I) The component (C) is contained as a surface treatment agent for the component (D) (ii) The component (C) is contained alone in the resin composition (iii) The component (C) is a surface treatment agent for the component (D) Contained and contained in resin composition by component (C) alone “(C) component is contained as a surface treatment agent for component (D)” means that (D) component is surface treated with component (C) It represents being done. In this case, the component (C) is usually on the surface of the component (D). In addition, “(C) component alone contained in resin composition” means that (C) component is not contained as a surface treatment agent for (D) component. In addition, when (C) component does not contain as a surface treating agent of (D) component, (D) component is free in the resin composition, and it is effective for low roughness of the insulating layer surface. .

  When the component (C) is contained alone in the resin composition, the content of the component (C) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and 0.2% by mass or more. Further preferred. Although an upper limit is not specifically limited, 10 mass% or less is preferable, 8 mass% or less is more preferable, and 6 mass% or less is further more preferable.

  When the component (C) is contained as the surface treatment agent for the component (D), the degree of surface treatment with the component (C) is determined from the viewpoint of reducing the roughness of the insulating layer surface and the depth of the plating hole. Surface treatment is preferably performed with 0.2 to 5 parts by mass of component (C) with respect to 100 parts by mass, and surface-treated with 0.3 to 3 parts by mass of component (C). It is more preferable that the surface treatment is carried out with 0.5 to 2.5 parts by mass of component (C).

<(D) Inorganic filler>
The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica and alumina are particularly suitable. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

  The average particle size of the inorganic filler is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less, and even more preferably 1 μm from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. It is as follows. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.1 micrometer or more, More preferably, it is 0.3 micrometer or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “YC100C”, “YA050C”, “YA050C-MJE”, “YA010C” manufactured by Admatechs, manufactured by Denki Kagaku Kogyo Co., Ltd. “UFP-30”, “Silfil NSS-3N”, “Silfil NSS-4N”, “Silfil NSS-5N” manufactured by Tokuyama Corporation, “SO-C4”, “SO-C2” manufactured by Admatechs Corporation, "SO-C1" etc. are mentioned.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd. or the like can be used.

  The inorganic filler is preferably surface-treated with a surface treatment agent. Examples of the surface treatment agent include the component (C) and a surface treatment agent other than the component (C) (hereinafter also referred to as “other surface treatment agent”). The inorganic filler may be surface-treated with the component (C) or may be surface-treated with another surface treatment agent. From the viewpoint of increasing the moisture resistance and dispersibility, and reducing the roughness of the insulating layer surface and the plating depth, it is preferable that the surface is treated with the component (C), and other surfaces in addition to the component (C) It may be surface-treated with a treatment agent.

  Examples of other surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. These may be used alone or in combination of two or more. Examples of such other commercially available surface treatment agents include “KBM-403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM-” manufactured by Shin-Etsu Chemical Co., Ltd. 803 "(3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd." KBE-903 "(3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd." KBM-573 "(N-phenyl) -3-aminopropyltrimethoxysilane), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Kogyo Co., Ltd. and the like can be mentioned.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.05 mg / m ² or more, more preferably 0.1 mg / m ² or more, and 0.2 mg / m ^2. The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of preventing an increase in the melt viscosity of the resin varnish or the sheet form. preferable. The amount of carbon per unit surface area of the inorganic filler can be measured according to the method described in <Calculation of amount of carbon per unit surface area> described later.

  The content of the inorganic filler in the resin composition is preferably 60% by mass or more, more preferably 65% by mass or more, and further preferably 70% by mass or more from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. The upper limit of the content of the inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less, from the viewpoint of the mechanical strength of the insulating layer. When (D) component is surface-treated with (C) component, content of the said inorganic filler is content including (C) component.

<(E) Thermoplastic resin>
The resin composition of the present invention may contain (E) a thermoplastic resin in addition to the components (A) to (D).

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

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

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resins), “YX8100BH30” (bisphenol S skeleton-containing phenoxy resin), and “YX6954BH30” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “YX6954BH30”, “YX7553BH30”, “YL7769BH30” manufactured by Mitsubishi Chemical Corporation, “YL6794BH30”, “YL7213BH30”, “YL7290BH30”, “YL7482BH30” and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. , Sreck BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more 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% by mass to 10% by mass, more preferably 0.6% by mass to 5% by mass, and still more preferably 0.8%. It is 7 mass%-3 mass%.

<(F) Curing accelerator>
The resin composition of the present invention may contain (F) a curing accelerator in addition to the components (A) to (D).

  Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

  Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 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 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

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

  Although content of the hardening accelerator in a resin composition is not specifically limited, 0.01 mass%-9 mass% are preferable when the non-volatile component of an epoxy resin and a hardening | curing agent is 100 mass%.

<(G) Flame retardant>
The resin composition of the present invention is excellent in flame retardancy even if it does not contain a flame retardant, but may contain (G) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

  Commercially available products may be used as the flame retardant, for example, “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi 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 mass%-10 mass% are further more preferable.

<(H) Organic filler>
From the viewpoint of improving elongation, the resin composition may include (H) an organic filler. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.

  As the rubber particles, commercially available products may be used, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan Co., Ltd., “AC3816N” manufactured by Ganz Kasei Co., Ltd., and the like.

  When the resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably 0.8%. 3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.

<(I) Optional additive>
The resin composition may further contain other additives as necessary. Examples of such other additives include organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds, And resin additives such as thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents.

  Moreover, it is preferable that the resin composition further contains a polyimide resin having a polybutadiene structure, a urethane structure, an imide structure, and a phenol structure at the molecular end from the viewpoint of producing a flexible printed wiring board. When the polyimide resin is contained, the content is preferably 10% by mass to 85% by mass, more preferably 15% by mass to 50% by mass, and still more preferably 20% by mass to 30% by mass.

  The details of the polyimide can be referred to the description in International Publication No. 2008/153208, the contents of which are incorporated herein.

  The resin composition of the present invention provides an insulating layer having excellent surface roughness, peel strength, plating bore depth, component embedding property, and flame retardancy. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and interlayer insulation of the printed wiring board. It can be more suitably used as a resin composition for forming a layer (a resin composition for an interlayer insulating layer of a printed wiring board). Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board.

[Sheet laminated material]
The resin composition of the present invention can be used by being applied in a varnish state, but industrially, it is generally preferable to use it in the form of a sheet-like laminate material containing the resin composition.

  As a sheet-like laminated material, the following resin sheet and prepreg are preferable.

  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 from the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. In particular, in the present invention, since the plating depth can be suppressed small, it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

  When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, “Lumirror T6AM” manufactured by Toray Industries, Inc., and the like.

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

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

  Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol, etc. Carbitols, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  In the resin sheet, a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches. The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

  In one embodiment, the prepreg is formed by impregnating the sheet-like fiber base material with the resin composition of the present invention.

  The sheet-like fiber base material used for a prepreg is not specifically limited, What is used normally as base materials for prepregs, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fiber base material is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. In particular, in the present invention, since the plating depth can be suppressed small, it is preferably 30 μm or less, more preferably 20 μm or less, and even more preferably 10 μm or less. Although the minimum of the thickness of a sheet-like fiber base material is not specifically limited, Usually, it may be 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

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

  The thickness of the prepreg can be in the same range as the resin composition layer in the resin sheet described above.

  The minimum melt viscosity of the resin composition layer (resin composition impregnated in the sheet-like fiber substrate in the case of a prepreg) in the sheet-like laminated material is preferably 12000 poise (1200 Pa · s) from the viewpoint of obtaining good component embedding properties. Hereinafter, it is more preferably 10000 poise (1000 Pa · s) or less, further preferably 8000 poise (800 Pa · s) or less, 5000 poise (500 Pa · s) or less, or 4000 poise (400 Pa · 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 250 poise (25 Pa) from the viewpoint of stably maintaining the thickness even if the resin composition layer is thin. -S) or more is more preferable.

  The minimum melt viscosity of the resin composition layer refers to the minimum 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 in the initial stage as the temperature rises, and then exceeds a certain level, the melt viscosity increases as the temperature rises. To do. The minimum melt viscosity refers to the melt viscosity at such a minimum point. The minimum melt viscosity of the resin composition layer can be measured by a dynamic viscoelasticity method. For example, it can be measured according to the method described in <Measurement of minimum melt viscosity of resin composition layer> described later.

  A cured product of the resin composition (or resin composition layer) of the present invention (for example, thermosetting the resin composition at 190 ° C. for 90 minutes) exhibits the property of being excellent in flame retardancy. The flame retardancy is preferably V-0 based on the UL-94V standard or better. The evaluation of flame retardancy can be measured according to the method described in <Flame retardance evaluation> described later.

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

For example, the printed wiring board of the present invention can be produced by a method including the following steps (I) and (II) using the above-described resin sheet.
(I) A step of laminating a resin sheet on an inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) A step of thermosetting the resin composition layer to form an insulating layer

  The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with a built-in component may be used (the conductor layer is also referred to as a wiring layer).

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

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

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

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C.) and the curing 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 cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used in the production of printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V).

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent (roughening liquid), For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP”, “Concentrate Compact P”, and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. Can be mentioned. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 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 neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

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

  The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The conductor layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.

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

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

  In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  Since the resin composition of the present invention provides an insulating layer having good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board.

As a method of manufacturing such a component built-in circuit board,
(I) an inner substrate having first and second opposing main surfaces and having a cavity penetrating between the first and second main surfaces, and a second main surface of the inner substrate; Preparing a component tacking inner layer substrate, comprising: a tacking material comprising: and a component tacked with the tacking material inside the cavity of the inner layer substrate;
(Ii) a step of laminating the resin sheet of the present invention so that the resin composition layer is bonded to the first main surface of the inner layer substrate;
(Iii) a step of peeling the temporary attachment material from the second main surface of the inner layer substrate;
(Iv) a step of laminating the resin sheet so that the resin composition layer is bonded to the second main surface of the inner layer substrate, and (v) a step of thermosetting the resin composition layer.

  As shown in FIG. 1, the component temporary bonding inner layer substrate 100 (also referred to as “cavity substrate”) has first and second main surfaces 11 and 12 that face each other, and the first and second main surfaces. Inner layer substrate 1 in which a cavity 1a penetrating between the surfaces is formed, temporary attachment material 2 bonded to second main surface 12 of inner layer substrate 1, and temporary attachment material 2 inside cavity 1a of inner layer substrate 1 And the part 3 temporarily attached. The inner layer substrate 1 may include circuit wiring 4 such as via wiring and surface wiring.

  The cavity formed in the inner layer substrate can be formed by a known method using, for example, a drill, a laser, plasma, an etching medium or the like in consideration of the characteristics of the inner layer substrate. A plurality of cavities may be formed at a predetermined interval, and the opening shape of the cavity is not particularly limited, and may be an arbitrary shape such as a rectangle, a circle, a substantially rectangle, or a substantially circle.

  The tacking material is not particularly limited as long as it has an adhesive surface exhibiting sufficient tackiness for tacking a component, and any conventionally known tacking material may be used in the manufacture of the component built-in circuit board. Examples of the tacking material include PFDKE-1525TT (polyimide film with adhesive) manufactured by Arisawa Manufacturing Co., Ltd., and UC series (UV tape for wafer dicing) manufactured by Furukawa Electric Co., Ltd.

  The part is temporarily attached to the adhesive surface of the temporary attachment material exposed through the cavity. As the component, an appropriate electrical component may be selected according to desired characteristics, and examples thereof include passive components such as capacitors, inductors, resistors, multilayer ceramic capacitors, and active components such as semiconductor bare chips. The same part may be used for all cavities, or different parts may be used for each cavity.

  Step (ii) is a step of laminating the resin sheet of the present invention so that the resin composition layer is bonded to the first main surface of the inner layer substrate. The conditions for laminating the first main surface and the resin sheet are the same as those in the above-described step (I), and the preferred range is also the same.

  After the resin composition layer is laminated on the first main surface of the inner layer substrate, the resin composition layer may be thermoset. The conditions for thermosetting the resin composition layer are the same as the conditions of the above-described step (II), and the preferred range is also the same.

  Step (iii) is a step of peeling the temporary attachment material from the second main surface of the inner layer substrate. The peeling of the tacking material may be performed according to a conventionally known method according to the type of the tacking material.

  Step (iv) is a step of laminating the resin sheet such that the resin composition layer is bonded to the second main surface of the inner layer substrate. The conditions for laminating the second main surface and the resin sheet are the same as the conditions for the step (I) described above, and the preferred range is also the same. The resin composition layer in the step (iv) may be the same resin composition layer as the resin composition layer in the step (ii), or may be a different resin composition layer.

  Step (v) is a step of thermosetting the resin composition layer. The conditions for thermosetting the resin composition layer are the same as the conditions of the above-described step (II), and the preferred range is also the same.

  The component built-in circuit board manufacturing method further includes a step of drilling the insulating layer (drilling step), a step of roughening the surface of the insulating layer, and a step of forming a conductor layer on the roughened insulating layer surface. May be included. These steps are as described above.

  The printed wiring board of this invention may be an aspect provided with the insulating layer which is the hardened | cured material of the resin composition layer of the resin sheet of this invention, and the embedding type wiring layer embedded in the insulating layer.

As a manufacturing method of such a printed wiring board,
(1) preparing a substrate with a wiring layer having an inner layer substrate and a wiring layer provided on at least one surface of the substrate;
(2) The step of laminating the resin sheet of the present invention on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer and thermally curing to form an insulating layer;
(3) a step of interconnecting the wiring layers, and (4) a step of removing the base material.

  It is preferable to have a metal layer made of copper foil or the like on both surfaces of the inner layer substrate used in this manufacturing method, and it is more preferable that the metal layer has a structure in which two or more metal layers are laminated. For the details of the step (1), a dry film (photosensitive resist film) is laminated on the inner layer substrate, and exposed and developed under a predetermined condition using a photomask to form a pattern dry film. A wiring layer is formed by electroplating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off.

  The lamination conditions of the inner layer substrate and the dry film are the same as the conditions of the step (II) described above, and the preferred range is also the same.

  After laminating the dry film on the inner layer substrate, exposure and development are performed under predetermined conditions using a photomask in order to form a desired pattern on the dry film.

  The line (circuit width) / space (inter-circuit width) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 18/18 μm or less (pitch 36 μm or less), More preferably, it is 15/15 μm or less (pitch 30 μm or less). The lower limit of the line / space ratio of the wiring layer is not particularly limited, but is preferably 0.5 / 0.5 μm or more, more preferably 1/1 μm or more. The pitch need not be the same throughout the wiring layer.

  After forming the dry film pattern, a wiring layer is formed, and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film having a desired pattern as a plating mask.

  The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The wiring layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A nickel alloy and a copper / titanium alloy).

  The thickness of the wiring layer depends on the design of the desired printed wiring board, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, and even more preferably 10 to 20 μm, or 15 μm.

  After forming the wiring layer, the dry film is peeled off. Peeling of the dry film can be performed by a known method. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern.

  Step (2) is a step of forming an insulating layer by laminating a resin sheet on a substrate with a wiring layer so that the wiring layer is embedded in the resin composition layer and thermosetting the resin sheet. The lamination conditions of the base material with a wiring layer and the resin sheet are the same as the conditions of the step (II) described above, and the preferable range is also the same.

  The step (3) is not particularly limited as long as the wiring layers can be connected to each other, but a step of forming a via hole in the insulating layer to form a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is at least one of these steps. The process of forming the via hole in the insulating layer and forming the conductor layer is as described above.

  The insulating layer polishing method or grinding method is not particularly limited as long as the printed wiring layer can be exposed and the polishing or grinding surface is horizontal, and conventionally known polishing methods or grinding methods can be applied, Examples thereof include a chemical mechanical polishing method using a chemical mechanical polishing apparatus, a mechanical polishing method such as buffing, and a surface grinding method by rotating a grinding wheel.

  Step (4) is a step of removing the inner substrate and forming the printed wiring board of the present invention. The method for removing the inner layer substrate is not particularly limited. In a preferred embodiment, the inner substrate is peeled from the printed wiring board at the interface of the metal layer on the inner substrate, and the metal layer is etched away with, for example, an aqueous copper chloride solution.

  In another embodiment, the printed wiring board of the present invention can be manufactured using the prepreg described above. The manufacturing method is basically the same as when using a resin sheet.

  The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. For this reason, the characteristic that it is excellent in component embedding is shown. That is, the component built-in circuit board manufactured using the sheet-like laminated material of the present invention can be configured such that the outer peripheral portion of the component is covered with the resin composition in all the cavities. The evaluation of component embeddability can be measured according to the method described in <Evaluation of component embeddability> described later.

  Since the printed wiring board of this invention contains the insulating layer formed with the hardened | cured material of the resin composition of this invention, roughness can be made low. Specifically, the arithmetic average roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment show 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, but may be 100 nm or more. The root mean square roughness (Rq) of the insulating layer surface is preferably 600 nm or less, more preferably 550 nm or less, and further preferably 530 nm or less. The lower limit is not particularly limited, but may be 100 nm or more. Evaluation of arithmetic mean roughness (Ra) and root mean square roughness (Rq) can be measured using a commercially available non-contact type surface roughness meter, and, for example, described later (arithmetic mean roughness ( Ra), measurement of root mean square roughness (Rq)).

  The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention. For this reason, the peel strength (peeling strength) between the insulating layer and the conductor layer after the roughening treatment shows a good result. The peel strength is preferably 0.3 kgf / cm or more, more preferably 0.40 kgf / cm or more, and still more preferably 0.45 kgf / cm or more. Although an upper limit is not specifically limited, It can be 1.2 kgf / cm or less, 0.9 kgf / cm or less, etc. In the present invention, although the arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer after the roughening treatment are low, a conductor layer exhibiting such a high peel strength can be formed. For this reason, it greatly contributes to the fine wiring of the printed wiring board. The peel strength can be evaluated according to the method described later (Measurement of peel strength).

  The insulating layer formed with the resin composition (or resin composition layer) of the present invention exhibits a good depth of plating. The plating depth is preferably 3.0 μm or less, more preferably 2.5 μm or less, and more preferably 2.0 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. As an embodiment, in the present invention, since the plating grind depth is low, even an insulating layer manufactured using a resin composition layer having a thickness of 10 μm or less has insulating properties, thereby printing. Significantly contributes to fine wiring and thinning of wiring boards. The evaluation of the plating bore depth can be measured according to the method described later (measurement of the plating bore depth).

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

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

<Calculation of carbon amount per unit surface area>
3 g of each of the following inorganic fillers was used as a sample. The sample and 30 g of MEK (methyl ethyl ketone) were placed in a centrifuge tube, stirred and suspended in solids, and irradiated with 500 W ultrasonic waves at 25 ° C. for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and 20 g of the supernatant was removed. Furthermore, 20 g of MEK was added, the solid content was suspended by stirring, and 500 W ultrasonic waves were irradiated at 25 ° C. for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and 26 g of the supernatant was removed. The remaining suspension was dried at 160 ° C. for 30 minutes. 0.3 g of this dried sample was accurately weighed in a measuring crucible, and a combustion aid (3.0 g of tungsten and 0.3 g of tin) was further placed in the measuring crucible. The measuring crucible was set in a carbon analyzer (“EMIA-321V2” manufactured by Horiba, Ltd.), and the amount of carbon was measured. The amount of carbon per unit surface area was calculated by dividing the measured value of the carbon amount by the specific surface area of the inorganic filler used.

<Used inorganic filler>
Inorganic filler 1: Spherical silica (“SO-C4” manufactured by Admatechs Co., Ltd., surface-treated with hexamethyldisilazane, average particle size of about 1 μm described by the manufacturer), 100 parts of 3, 3, 3 -Surface treatment with 1 part of trifluoropropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-7103). The amount of carbon per unit surface area was 0.25 mg / m ² .

Inorganic filler 2: spherical silica ("SO-C1" manufactured by Admatechs Co., Ltd., surface-treated with hexamethyldisilazane, manufacturer's average particle size of about 0.3 µm), 100 parts, Surface treated with 2 parts of 3-trifluoropropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-7103). The amount of carbon per unit surface area was 0.16 mg / m ² .

Inorganic filler 3: 3,3,3-trifluoropropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) for 100 parts of spherical alumina (“DAW-01” manufactured by Denka Co., Ltd., average particle size of about 1.5 μm described by the manufacturer) Surface treated with 1 part of Kogyo Co., Ltd., KBM-7103). The amount of carbon per unit surface area was 0.12 mg / m ² .

Inorganic filler 4: 3-glycidoxypropyl with respect to 100 parts of spherical silica ("SO-C4" manufactured by Admatechs Co., Ltd., surface-treated with hexamethyldisilazane, manufacturer's average particle size of about 1 µm) Surface treated with 1 part of trimethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.31 mg / m ² .

Inorganic filler 5: 3-aminopropyl with respect to 100 parts of spherical silica (“SO-C1” manufactured by Admatechs Co., Ltd., surface-treated with hexamethyldisilazane, manufacturer's average particle size of about 0.3 μm) Surface treated with 2 parts of trimethoxysilane (“KBM-903” manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of carbon per unit surface area was 0.23 mg / m ² .

Inorganic filler 6: acetoalkoxyaluminum diisopropylate (manufactured by Ajinomoto Fine Techno Co., Ltd.) with respect to 100 parts of spherical alumina ("DAW-01" manufactured by Denka Co., Ltd., average particle size of about 1.5 μm described by the manufacturer) "Plenact AL-M") Surface treated with 1 part. The amount of carbon per unit surface area was 0.15 mg / m ² .

Inorganic filler 7: Spherical silica ("SO-C4" manufactured by Admatechs Co., Ltd., surface-treated with hexamethyldisilazane, manufacturer's average particle size of about 1 µm), 100 parts of phenyltrimethoxysilane (Shin-Etsu) Surface treated with 1 part of KBM-103 manufactured by Chemical Industry Co., Ltd. The amount of carbon per unit surface area was 0.30 mg / m ² .

[Production of resin sheet]
Using the resin varnish (resin composition) prepared by the following procedure, resin sheets of Examples and Comparative Examples were produced.

<Preparation of resin varnish 1>
Bisphenol type liquid epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169, 1: 1 mixture of bisphenol A type and bisphenol F type) 4 parts, bixylenol type epoxy resin (Mitsubishi Chemical Corporation) 6 parts of “YX4000HK”, epoxy equivalent of about 185), 20 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., about 272) are mixed in a solvent mixture of 15 parts of solvent naphtha and 10 parts of cyclohexanone. It was dissolved by heating with stirring. After cooling to room temperature, there are 8 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%). , 4 parts of triazine skeleton-containing phenol novolak-based curing agent (“LA-7054” manufactured by DIC Corporation, MEK solution having a hydroxyl equivalent weight of about 125 and a solid content of 60%), naphthol-based curing agent (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) SN-495V ", hydroxyl group equivalent of about 231, MEK solution with 60% solid content) 10 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% solid content) 1 part, rubber particles (2 parts by Dow Chemical Japan Co., Ltd., EXL2655) and 190 parts of inorganic filler 1 were mixed and dispersed uniformly with a high-speed rotary mixer. And filtered through a ridge filter (ROKITECHNO made "SHP050"), to prepare a resin varnish 1.

<Preparation of resin varnish 2>
4 parts cyclohexanedimethanol type liquid epoxy resin (“ZX1658GS” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 135), 15 parts of bisphenol AF type epoxy resin (“YL7760” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238) , 15 parts of naphthalene type epoxy resin (“NSN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 330), and phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Co., Ltd.), 30% by mass of cyclohexanone: methyl ethyl ketone (MEK) 10 parts) was dissolved in a mixed solvent of 15 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, there are 8 parts of a triazine skeleton-containing cresol novolac-based curing agent (“LA-3018-50P” manufactured by DIC Corporation, hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%). , 12 parts of an active ester curing agent (“EXB-8000L-65M” manufactured by DIC Corporation, MEK solution having an active group equivalent of about 220 and 65% by mass of non-volatile components), an amine curing accelerator (4-dimethylaminopyridine ( DMAP), MEK solution with a solid content of 5% by mass) 1.5 parts and 125 parts of inorganic filler 2 are mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter ("SHP030" manufactured by ROKITECHNO). Resin varnish 2 was prepared.

<Preparation of resin varnish 3>
50 parts of component (i) prepared as described below, 2 parts of naphthylene ether type epoxy resin (DIC Corporation "EXA-731-G4", epoxy equivalent of about 213), bisphenol AF type epoxy resin (Mitsubishi Chemical) 4 parts of “YL7760” manufactured by Co., Ltd., and 2 parts of flame retardant (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.) are mixed into 10 parts of solvent naphtha and 5 parts of cyclohexanone. It was dissolved by heating with stirring. There, 2 parts of an active ester curing agent (“EXB-8000L-65M” manufactured by DIC Corporation, an MEK solution having an active group equivalent of about 220 and 65% by mass of a non-volatile component), an imidazole curing accelerator (Shikoku Chemical Industries ( 1 part of “1B2PZ” 1-benzyl-2-phenylimidazole, 5% solid content MEK solution) and 125 parts of inorganic filler 3 were mixed and dispersed uniformly with a high-speed rotary mixer, and a cartridge filter ( The resin varnish 3 was prepared by filtration through “SHP050” manufactured by ROKITECHNO.

(Preparation of component (i))
In a reaction vessel, 50 g of G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content 100 mass%, Nippon Soda Co., Ltd.) 23.5 g of solvent naphtha (aromatic hydrocarbon-based mixed solvent: “Ipsol 150” manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and dissolved uniformly. When the temperature became uniform, the temperature was raised to 50 ° C., and while further stirring, 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added and the reaction was carried out for about 3 hours. The reaction was then cooled to room temperature before 8.96 g benzophenonetetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g triethylenediamine, and ethyl diglycol. 40.4 g of acetate (manufactured by Daicel Corporation) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak at 2250 cm ⁻¹ was confirmed by FT-IR. Upon confirming the disappearance of the NCO peak, the reaction is considered to be the end point of the reaction. The reaction product is cooled to room temperature and then filtered through a 100 mesh filter cloth to obtain a polymer resin having an imide skeleton, a urethane skeleton, and a butadiene skeleton (component (i)) Got. The analysis results of this polymer resin (component (i)) are as follows.
Viscosity: 7.5 Pa · s (25 ° C, E-type viscometer)
Acid value: 16.9 mgKOH / g
Solid content: 50% by mass
Number average molecular weight: 13723
Glass transition temperature: -10 ° C
Content ratio of polybutadiene structure part: 50 / (50 + 4.8 + 8.96) × 100 = 78.4% by mass

<Preparation of resin varnish 4>
In the preparation of the resin varnish 1, 190 parts of the inorganic filler 1 was changed to 190 parts of the inorganic filler 4, and 15 parts of solvent naphtha was changed to 20 parts. A resin varnish 4 was prepared in the same manner as the resin varnish 1 except for the above items.

<Preparation of resin varnish 5>
In the preparation of resin varnish 2, 125 parts of inorganic filler 2 was changed to 125 parts of inorganic filler 5 and 15 parts of solvent naphtha was changed to 20 parts. A resin varnish 5 was prepared in the same manner as the resin varnish 2 except for the above items.

<Preparation of resin varnish 6>
In the preparation of the resin varnish 3, 125 parts of the inorganic filler 3 was changed to 125 parts of the inorganic filler 6. A resin varnish 6 was prepared in the same manner as the resin varnish 3 except for the above items.

<Preparation of resin varnish 7>
In the preparation of the resin varnish 1, 190 parts of the inorganic filler 1 was changed to 190 parts of the inorganic filler 7. A resin varnish 7 was prepared in the same manner as the resin varnish 1 except for the above items.

  The materials used for the production of each resin varnish and the blending amount (parts by mass of nonvolatile components) are shown in the following table. The contents (% by mass) in the non-volatile components of the liquid epoxy resin and (C) inorganic filler are also shown.

<Examples 1-3 and Comparative Examples 1-4: Production of Resin Sheet>
As a support, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc.) having a release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec Corporation), a thickness of 38 μm, a softening point of 130 ° C., “release” Type PET ").

  Each resin varnish is uniformly applied with a die coater so that the thickness of the resin composition layer after drying is 25 μm on the release PET, and dried at 80 ° C. to 110 ° C. for 4 minutes. A resin composition layer was obtained on top. Next, a polypropylene film (“Alphan MA-430” manufactured by Oji F-Tex Co., Ltd., thickness 20 μm) as a protective film is bonded to the surface of the resin composition layer not bonded to the release PET. Laminated so that. Thereby, the resin sheet which consists of order of mold release PET, a resin composition layer, and a protective film was obtained.

<Measurement of minimum melt viscosity of resin composition layer>
Only the resin composition layer was peeled from the release PET, and compressed with a mold to prepare measurement pellets (diameter 18 mm, 1.2 g to 1.3 g). Using pellets for measurement, using a dynamic viscoelasticity measuring device (“Rheosol-G3000” manufactured by UBM Co., Ltd.), using a parallel plate having a diameter of 18 mm for 1 g of the sample resin composition layer, The temperature was raised from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./min, and the dynamic viscoelastic modulus was measured under the measurement conditions of a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, and a strain of 1 deg. The melt viscosity was calculated and the results are shown in the table below.

<Evaluation of component embedding>
Using the resin sheets prepared in Examples and Comparative Examples, a component provisional circuit board was prepared according to the following procedure, and component embedding was evaluated.

(1) Preparation of component temporary mounting circuit board (cavity board) Glass cloth base BT resin double-sided copper clad laminate (copper foil thickness 18 μm, board thickness 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd.) Cavities of 0.7 mm × 1.1 mm were formed at a 3 mm pitch on the entire surface of 255 mm × 340 mm size. Next, both sides are etched by 1 μm with a micro-etching agent (“CZ8100” manufactured by Mec Co., Ltd.) to roughen the copper surface, and further subjected to rust prevention (“CL8300” manufactured by Mec Co., Ltd.). Dry at 30 ° C. for 30 minutes.

(2) Preparation of component temporary circuit board A batch of 25 μm thick polyimide film with adhesive (38 μm polyimide thickness, manufactured by Arisawa Manufacturing Co., Ltd., “PFDKE-1525TT”) is applied to one side of the substrate obtained in (1). Using a pressure-type vacuum press laminator (Nichigo Morton Co., Ltd. 2-stage build-up laminator “CVP700”), the pressure-sensitive adhesive was disposed so as to be bonded to the substrate and laminated on one side. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 80 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, multilayer ceramic capacitor parts (1005 = 1 × 0.5 mm size, thickness 0.14 mm) were temporarily attached to the cavities one by one to produce a part temporary circuit board (cavity board).

(3) Component embedding evaluation test Using a batch-type vacuum pressurization laminator (Nichigo-Morton Co., Ltd. 2-stage buildup laminator “CVP700”), a protective film was formed from the resin sheets prepared in Examples and Comparative Examples. The peeled and exposed resin composition layer and the surface of the component temporary circuit board (cavity substrate) prepared in (2) on the side opposite to the pressure-sensitive adhesive polyimide film placement surface were laminated so as to be bonded. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheets were smoothed by hot pressing at 120 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure. Evaluation board | substrate A was produced by peeling the polyimide film with an adhesive from the component provisional circuit board cooled to room temperature. From the surface of the evaluation substrate A from which the polyimide film was peeled off, the resin flow in the cavity was observed with an optical microscope (150 times) (performed for 10 cavities), the component embedding property was evaluated according to the following criteria, and the result was It is shown in the table below.
(Evaluation criteria)
○: In all the cavities, the outer peripheral portion of the multilayer ceramic capacitor component is covered with resin.
X: Some of the cavities have voids or are not embedded with resin in the outer peripheral portion of the multilayer ceramic capacitor component.
It was judged.

<Evaluation of Peeling Strength (Peel Strength), Roughness (Arithmetic Average Roughness (Ra), Root Mean Square Roughness (Rq)), and Peeling Depth of Plating Conductor Layer>
Using the resin sheets prepared in Examples and Comparative Examples, measurement substrates B and C were prepared according to the following procedure, and peel strength, roughness, and plating drilling depth were evaluated.

(1) Substrate treatment of laminated board Glass cloth base epoxy resin double-sided copper-clad laminated board (copper foil thickness 18μm, substrate thickness 0.3mm, R5715ES manufactured by Matsushita Electric Works Co., Ltd.) The copper surface was roughened by etching with a treatment agent (CZ8100) at 1 μm.

(2) Lamination of resin sheet The resin composition layer exposed by peeling off the protective film from the resin sheets prepared in Examples and Comparative Examples was subjected to a batch type vacuum pressure laminator (Nichigo-Morton Co., Ltd. 2-stage build-up). A laminator “CVP700”) was used to laminate on both sides of the substrate so that the resin composition layer was bonded to the substrate. Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 120 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheets were smoothed by hot pressing at 120 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(3) Thermosetting of resin composition layer After laminating the resin sheets, the resin composition layer was thermosetting (100 ° C for 30 minutes, then 175 ° C for 30 minutes) to form insulating layers on both sides of the substrate. At that time, for Examples 1 and 2 and Comparative Examples 1, 2, and 4, the resin composition layer was heat-cured in a state where release PET as a support was attached. For Example 3 and Comparative Example 3, the resin composition layer was thermally cured after peeling the release PET as the support.

(4) Roughening treatment The laminated board on which the insulating layer is formed is a swelling liquid, Swelling Dip Securigans P (glycol ethers, aqueous solution of sodium hydroxide) containing diethylene glycol monobutyl ether of Atotech Japan K.K. For 5 minutes at 60 ° C. Then the roughening solution, Atotech Japan Concentrate Compact P of Co. in _{(KMnO 4:: 60g / L} , NaOH 40g / L aqueous solution) was immersed for 15 minutes at 80 ° C. (Example 2, Comparative Example 2 was immersed at 80 ° C. for 20 minutes). Finally, as a neutralizing solution, it was immersed for 5 minutes at 40 ° C. in Reduction Sholysin Securigant P (an aqueous solution of sulfuric acid) of Atotech Japan Co., Ltd. After drying at 80 ° C. for 30 minutes, this substrate was designated as an evaluation substrate B.

(5) Plating by semi-additive method The evaluation substrate B produced in (4) is immersed in an electroless plating solution containing PdCl ₂ at 40 ° C. for 5 minutes, and then is immersed in an electroless copper plating solution at 25 ° C. at 20 ° C. Immerse for a minute. After annealing for 30 minutes at 150 ° C., an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 30 μm. Next, the substrate obtained by performing the annealing treatment at 190 ° C. for 60 minutes was used as an evaluation substrate C.

(Measurement of arithmetic average roughness (Ra), root mean square roughness (Rq))
Using a non-contact type surface roughness meter (WYKO NT3300 manufactured by BEIKO INSTRUMENTS Co., Ltd.) for the evaluation substrate B, Ra values and Rq values are obtained by numerical values obtained with a measurement range of 121 μm × 92 μm using a VSI contact mode and a 50 × lens. Asked. The average value of 10 points was calculated for each, and the results are shown in the following table.

(Measurement of peel strength)
The conductor layer of the evaluation substrate C is cut with a 10 mm width and a length of 100 mm, and one end is peeled off to grasp the grip (TSE, Inc., Autocom type testing machine AC-50C-SL). And measured the load (kgf / cm (N / cm)) when 35 mm was peeled in the vertical direction at a speed of 50 mm / min at room temperature (25 ° C.), and the results are shown in the following table.

(Measurement of drilling depth of plating)
The evaluation substrate C was subjected to cross-sectional observation using a FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.). Specifically, a cross-section in the direction perpendicular to the surface of the evaluation substrate C is cut out by FIB (focused ion beam), and a cross-sectional SEM image of the vicinity of the interface between the plating and the roughened cured body (insulating layer) (observation width 7.5 μm) Observation magnification × 36000) was obtained. For each sample, 10 randomly selected cross-sectional SEM images were obtained, and the maximum value (μm) of the copper plating depth was measured.

<Evaluation of flame retardancy>
(1) Lamination of resin sheet The resin composition layer exposed by peeling off the protective film from the resin sheets prepared in Examples and Comparative Examples was subjected to a batch-type vacuum pressure laminator (Nichigo-Morton Co., Ltd. 2-stage build-up). Using a laminator “CVP700”, the resin composition layer was laminated on both sides of the laminate so that the resin composition layer was joined to the laminate (no copper foil, substrate thickness 0.2 mm, 679FG manufactured by Hitachi Chemical Co., Ltd.). Lamination was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated resin sheets were smoothed by hot pressing at 120 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure.

(2) Curing of resin composition layer After laminating resin sheets, the release PET as a support is peeled off, the resin composition layer is thermally cured (at 90 ° C. for 90 minutes), and cured products are applied to both sides of the laminate. Formed.

(3) Flame retardant test It was carried out in accordance with UL-94V standards. The obtained laminate (thickness: about 380 μm) was cut to a size of 12.7 mm × 127 mm and an edge of 1.27 mm, treated in a 70 ± 1 ° C. oven for 168 hours, and then released in a desiccator for 4 hours or more. It cooled and obtained the test piece.

The burner was moved directly under the obtained test piece, the flame was indirectly flamed at the center of the lower end of the test piece for 10 seconds, and the subsequent burning time was measured. The indirect flame was fired again for 10 seconds, and the subsequent combustion time was measured. This was repeated 5 times and evaluated based on the following criteria.
(Evaluation criteria)
V-0: Combustion does not fall, test piece is not burned, test piece burning time is 50 seconds or less V-1: Combustion is not dropped, test piece is not burnt, test piece burn time is 50 seconds Exceeding 250 seconds or less Not: Combustion dropping, burning of test piece, or burning time of test piece exceeds 250 seconds

  In Examples 1 to 3 using the resin composition containing the component (C), the part embedding property, the arithmetic average roughness (Ra), the root mean square roughness (Rq), the peel strength, the depth of plating plating, and the difficulty It turns out that it is excellent in flammability.

  Comparative Example 1 using an epoxy silane coupling agent (KBM-403) instead of the component (C) is more likely to aggregate than Examples 1 to 3, resulting in a higher minimum melt viscosity. It can be seen that the embedding property is inferior, and that the arithmetic average roughness (Ra), the root mean square roughness (Rq), the plating grind depth, and the flame retardance are also inferior.

  In Comparative Example 2 using an aminosilane coupling agent (KBM-903) instead of the component (C), the plating grind depth is lowered by coupling the amino group with a resin such as the component (A). From the fact that the minimum melt viscosity is high, it can be seen that the part embedding property is poor. Moreover, it turns out that a flame retardance is also inferior compared with Examples 1-3.

  In Comparative Example 3 using an aluminum coupling agent (Plenact AL-M) instead of the component (C), the component embedding property is good because the minimum melt viscosity is low, but the arithmetic average roughness (Ra), It can be seen that the root-mean-square roughness (Rq), the plating grind depth, and the flame retardancy are inferior.

  In Comparative Example 4 using the silane compound (KBM-103) instead of the component (C), the silane compound does not have a reactive group, so it is not coupled with the resin such as the component (A), and the plating depth is too small. It turns out that becomes high. Moreover, it turns out that arithmetic mean roughness (Ra), a root mean square roughness (Rq), plating grind depth, and a flame retardance are also inferior compared with Examples 1-3.

100 Component temporary bonding inner layer substrate (cavity substrate)
DESCRIPTION OF SYMBOLS 1 Inner layer board | substrate 1a Cavity 11 1st main surface 12 2nd main surface 2 Tacking material 3 Component 4 Circuit wiring

Claims (15)

  A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a fluorine atom-containing alkoxysilane compound, and (D) an inorganic filler.   The resin composition according to claim 1, wherein the content of the component (D) is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass.   (D) The resin composition of Claim 1 or 2 whose average particle diameter of a component is 0.01 micrometer-2 micrometers.   The resin composition according to any one of claims 1 to 3, wherein the component (D) is silica or alumina.   (C) The resin composition of any one of Claims 1-4 whose number of the fluorine atoms in 1 molecule of components is 1-10.   (C) The resin composition of any one of Claims 1-5 whose number of the alkoxy groups in 1 molecule of components is 1-5.   The resin composition according to any one of claims 1 to 6, wherein the component (C) is 3,3,3-trifluoropropyltrimethoxysilane.   The resin composition according to any one of claims 1 to 7, wherein the component (D) is surface-treated with the component (C).   The resin composition according to any one of claims 1 to 8, which is used for forming an insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 9, which is for a buildup layer of a printed wiring board.   The sheet-like laminated material containing the resin composition of any one of Claims 1-10.   The sheet-like laminated material containing the resin composition layer formed with the resin composition of any one of Claims 1-10.   The sheet-like laminated material according to claim 12, wherein the resin composition layer has a thickness of 10 μm or less.   The printed wiring board containing the insulating layer formed with the hardened | cured material of the resin composition of any one of Claims 1-10.   A semiconductor device comprising the printed wiring board according to claim 14.

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