CN116656085A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116656085A
CN116656085A CN202310142718.3A CN202310142718A CN116656085A CN 116656085 A CN116656085 A CN 116656085A CN 202310142718 A CN202310142718 A CN 202310142718A CN 116656085 A CN116656085 A CN 116656085A
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China
Prior art keywords
resin composition
resin
mass
composition according
epoxy resin
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CN202310142718.3A
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Chinese (zh)
Inventor
西村嘉生
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN116656085A publication Critical patent/CN116656085A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/296—Organo-silicon compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a conjugated diene-aromatic vinyl copolymer resin which contains alkoxysilyl groups and can be hydrogenated.

Description

Resin composition
Technical Field
The present invention relates to a resin composition. The present invention further relates to a cured product of the resin composition; a sheet-like laminate and a resin sheet each comprising the resin composition; and a printed wiring board and a semiconductor device including an insulating layer formed of a cured product of the resin composition layer.
Background
As a technique for manufacturing a printed wiring board, a stack (build up) method of manufacturing a printed wiring board in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method based on the stacking method, in general, the insulating layer may be formed of a cured product obtained by curing a resin composition (patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2005-039247
Patent document 2: japanese patent No. 4503239
Patent document 3: japanese patent laid-open publication No. 2009-235165.
Disclosure of Invention
Problems to be solved by the invention
The cured product contained in the insulating layer is required to have a low dielectric loss tangent. However, when the composition of a resin composition comprising an epoxy resin and a curing agent is adjusted to reduce the dielectric loss tangent of the cured product, the cured product obtained is brittle, and cracks (fractures) tend to be easily generated in the cured product. For example, when an active ester-based curing agent is used as the curing agent, the dielectric loss tangent of the cured product can be reduced, but on the other hand, cracks are likely to occur in the cured product.
In order to suppress the above-mentioned cracks, the present inventors have attempted to blend a soft component such as polybutadiene or a rubber component into a resin composition. However, in the resin composition containing the conventional soft component in combination with the epoxy resin and the curing agent, it is difficult to uniformly disperse the soft component, and as a result, the dielectric loss tangent may be increased or the appearance of the resin varnish and the resin sheet may be deteriorated. Accordingly, it is desired to develop a resin composition which can give a cured product having a low dielectric loss tangent and excellent crack resistance. Here, "crack resistance" refers to a property that can suppress occurrence of cracks in a cured product of a resin composition.
The present invention has been made in view of the above problems, and an object thereof is to provide: a resin composition which can give a cured product having a low dielectric loss tangent and excellent crack resistance; a cured product of the resin composition; a sheet-like laminate containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; a semiconductor device provided with the printed wiring board.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above-described problems. As a result, the present inventors have found that a resin composition comprising (a) an epoxy resin, (B) a curing agent, and (C) an alkoxysilyl group (alkoxlyyl) -containing conjugated diene-aromatic vinyl copolymer resin which can be hydrogenated can solve the aforementioned problems, and have completed the present invention. That is, the present invention includes the following aspects.
[1] A resin composition comprising (A) an epoxy resin, (B) a curing agent, and (C) a conjugated diene-aromatic vinyl copolymer resin containing an alkoxysilyl group and which can be hydrogenated;
[2] the resin composition according to [1], wherein the component (C) contains a conjugated diene compound unit (C1) which can be hydrogenated, and an aromatic vinyl compound unit (C2),
an alkoxysilyl group is bonded to a part or all of the conjugated diene compound units which may be hydrogenated in (c 1);
[3] the resin composition according to [2], wherein the conjugated diene compound unit (c 1) which can be hydrogenated is a butadiene unit which can be hydrogenated,
(c2) The aromatic vinyl compound unit is a styrene unit;
[4] the resin composition according to [2] or [3], wherein the conjugated diene compound unit (c 1) which can be hydrogenated contains a direct addition unit,
An alkoxysilyl group is bonded to a part or all of the side chains of the direct addition unit;
[5] the resin composition according to any one of [2] to [4], wherein the amount of the aromatic vinyl compound unit (C2) is 15 to 50 mass% inclusive, based on 100 mass% of the component (C);
[6] the resin composition according to any one of [1] to [5], wherein the component (C) contains (C3) an alkenylalkoxysilane unit;
[7] the resin composition according to any one of [1] to [6], wherein the component (C) comprises a structure represented by the following formula (1),
[ chemical formula 1]
(in the formula (1),
R 1 ～R 31 、R 34 ～R 40 r is R 43 ～R 45 Each independently represents a hydrogen atom, or a monovalent hydrocarbon group,
x represents a single bond or a divalent linking group,
R 32 、R 33 、R 41 r is R 42 Each independently represents a monovalent hydrocarbon group,
ar represents an aryl group optionally having a substituent,
a. b, c and d each independently represent an integer of 0 or more,
e and f represent integers of 0 or more satisfying e+f 1 or more,
g represents an integer of 1 or more,
h and i each independently represent an integer of 1 to 3,
the order of the repeating units a, b, c, d, e, f, and g is arbitrary. )
[8] The resin composition according to any one of [1] to [7], wherein the component (C) comprises a structure represented by the following formula (2),
[ chemical formula 2]
(in the formula (2),
y represents a single bond or a divalent hydrocarbon group,
R 46 r is R 47 Each independently represents a monovalent hydrocarbon group,
j and k each independently represent an integer of 0 or more,
l and m each independently represent an integer greater than 0,
n represents an integer of 1 to 3,
the order of the repeating units j, k, l, and m is arbitrary. )
[9] The resin composition according to any one of [1] to [8], wherein the amount of the component (C) is 0.01% by mass or more and 10% by mass or less relative to 100% by mass of the nonvolatile component of the resin composition;
[10] the resin composition according to any one of [1] to [9], wherein (B) the curing agent comprises an active ester-based curing agent;
[11] the resin composition according to any one of [1] to [10], which comprises (D) an inorganic filler;
[12] the resin composition according to [11], wherein the amount of the (D) inorganic filler is 50 mass% or more and 90 mass% or less relative to 100 mass% of the nonvolatile component of the resin composition;
[13] the resin composition according to any one of [1] to [12], which is used for forming an insulating layer;
[14] A cured product of the resin composition according to any one of [1] to [13 ];
[15] a sheet-like laminate comprising the resin composition of any one of [1] to [13 ];
[16] a resin sheet, comprising:
support body
A resin composition layer formed of the resin composition according to any one of [1] to [13] provided on the support;
[17] a printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [13 ];
[18] a semiconductor device comprising the printed wiring board according to [17 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides a resin composition which can give a cured product having a low dielectric loss tangent and excellent crack resistance; a cured product of the resin composition; a sheet-like laminate containing the resin composition; a resin sheet having a resin composition layer formed from the resin composition; a printed wiring board having an insulating layer containing a cured product of the resin composition; a semiconductor device provided with the printed wiring board.
Detailed Description
Hereinafter, the present invention will be described by way of examples and embodiments. However, the present invention is not limited to the embodiments and examples described below, and may be arbitrarily modified and implemented within the scope not exceeding the scope of the claims and their equivalents.
[ outline of resin composition ]
The resin composition according to one embodiment of the present invention comprises (A) an epoxy resin, (B) a curing agent, and (C) an alkoxysilyl group-containing, hydrogenated conjugated diene-aromatic vinyl copolymer resin. Hereinafter, the "(C) alkoxysilyl group-containing and hydrogenated conjugated diene-aromatic vinyl copolymer resin" as the component (C) may be referred to as a "(C) silicon-containing resin". The resin composition according to one embodiment of the present invention can provide a cured product having a low dielectric loss tangent and excellent crack resistance. Further, the cured product can generally form an insulating layer excellent in adhesion to the plated conductor layer. The plated conductor layer means a conductor layer formed by plating unless otherwise specified.
The present inventors speculate that the mechanism by which the aforementioned effects are obtained by the resin composition according to the present embodiment is as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
The silicon-containing resin (C) included in the resin composition according to the present embodiment has a soft conjugated diene-aromatic vinyl copolymer skeleton, and therefore the molecule itself is soft. Therefore, (C) the silicon-containing resin can relax stress in the cured product of the resin composition, and therefore cracking of the cured product can be suppressed. Further, the silicon-containing resin (C) has excellent compatibility with the epoxy resin (A) and the curing agent (B) because it contains an alkoxysilyl group. Therefore, the occurrence of phase separation in the cured product can be suppressed, and therefore, the formation of phase interfaces can be suppressed. In general, the phase interface tends to be a starting point of fracture due to stress concentration. However, since the formation of the phase interface can be suppressed in the cured product of the resin composition according to the present embodiment, the occurrence of the fracture starting from the phase interface can be suppressed, and the crack can be suppressed.
In addition, generally, the conjugated diene-aromatic vinyl copolymer may contain a carbon-carbon unsaturated bond in the skeleton. The carbon-carbon unsaturated bond may be oxidized to form a polar group, and thus may cause an increase in dielectric loss tangent due to the polar group. However, in the resin composition according to the present embodiment, since the proportion of the carbon-carbon unsaturated bond in the silicon-containing resin (C) is reduced by the inclusion of the alkoxysilyl group, the proportion of the polar group formed is reduced, and an increase in dielectric loss tangent due to the formation of the polar group can be suppressed. Therefore, with the resin composition according to the present embodiment, both improvement of crack resistance and reduction of dielectric loss tangent can be achieved.
In particular, when the (B) curing agent contains the (B-1) active ester curing agent, the dielectric loss tangent can be effectively suppressed. The (B-1) active ester curing agent does not generate polar groups by reaction with the (A) epoxy resin. Therefore, an increase in dielectric loss tangent due to the polar group can be effectively suppressed, and therefore, the dielectric loss tangent can be effectively reduced. In addition, the (B-1) active ester curing agent tends to have particularly low compatibility with conventional conjugated diene-aromatic vinyl copolymers. However, since the compatibility of the (C) silicon-containing resin with the (B-1) active ester-based curing agent is excellent, cracking can be effectively suppressed.
Further, the silicon-containing resin (C) has a function of improving toughness of a cured product of the resin composition because of its soft molecules. Therefore, even when the resin composition contains (D) the inorganic filler, the occurrence of cracks in the cured product can be suppressed. Conventionally, a cured product containing an inorganic filler tends to be brittle and easily cracked, and in view of this, it is advantageous that the resin composition according to the present embodiment can obtain a cured product in which occurrence of cracks can be suppressed even when (D) an inorganic filler is contained.
Further, since the toughness of the cured product of the resin composition can be improved as described above, the insulating layer containing the cured product is less likely to be broken by stress. Therefore, when the plated conductor layer is formed on the insulating layer, peeling of the plated conductor layer accompanied by breakage of the insulating layer can be suppressed. Therefore, the adhesion between the insulating layer and the plated conductor layer can be generally improved.
The resin composition according to one embodiment of the present invention may further contain optional components in addition to the components (a) to (C). Examples of the optional component include (D) an inorganic filler, (E) a thermoplastic resin, (F) a curing accelerator, (G) a radical polymerizable compound, and (H) an optional additive. The components contained in the resin composition according to one embodiment of the present invention will be described in detail below.
[ (A) epoxy resin ]
The resin composition according to one embodiment of the present invention contains (a) an epoxy resin as the component (a). (A) The epoxy resin may be a curable resin having an epoxy group.
Examples of the epoxy resin (a) include a bisxylenol (bisbenzoxol) type epoxy resin, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bisphenol AF type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenol type epoxy resin, a naphthol novolac (naphthalene type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butyl-catechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, a cresol novolac (cresol novolac) type epoxy resin, a phenol aralkyl type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin, an epoxy resin having a butadiene structure, a alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenyl ethane type epoxy resin, an isocyanatone type epoxy resin, and an phthalone type epoxy resin. (A) The epoxy resin may be used alone or in combination of 1 or more than 2.
From the viewpoint of obtaining a cured product excellent in heat resistance, the (a) epoxy resin preferably contains an epoxy resin containing an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatic and aromatic heterocyclic rings. Examples of the aromatic structure-containing 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, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisxylenol type epoxy resin, glycidyl amine type epoxy resin having an aromatic structure, glycidyl ester type epoxy resin having an aromatic structure, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having an aromatic structure, alicyclic epoxy resin having an aromatic structure, heterocyclic type epoxy resin, spiro ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, tetraphenyl ethylene type epoxy resin having an aromatic structure, and the like.
(A) The epoxy resin preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, particularly preferably 70% by mass or more, relative to 100% by mass of the total amount of the (a) epoxy resin.
(A) The epoxy resin includes an epoxy resin that is liquid at a temperature of 20 ℃ (hereinafter sometimes referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20 ℃ (hereinafter sometimes referred to as "solid epoxy resin"). (A) The epoxy resin may be a liquid epoxy resin alone, a solid epoxy resin alone, or a combination of a liquid epoxy resin and a solid epoxy resin. Among them, (a) the epoxy resin is preferably a combination of a liquid epoxy resin and a solid epoxy resin.
As the liquid epoxy resin, a liquid epoxy resin having 2 or more epoxy groups in 1 molecule is preferable.
The liquid epoxy resin is preferably bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, epoxy resin having a butadiene structure, epoxy resin having an alkylene oxide skeleton and a butadiene skeleton, epoxy resin having a fluorene structure, or dicyclopentadiene type epoxy resin. Among them, bisphenol a type epoxy resins and bisphenol F type epoxy resins are particularly preferable.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC corporation; "828US", "828EL", "jER828EL", "825", "EPIKOTE 828EL" manufactured by Mitsubishi chemical corporation (bisphenol A type epoxy resin); "jER807", "1750" manufactured by mitsubishi chemical company (bisphenol F type epoxy resin); "jER152" (phenol novolac type epoxy resin) manufactured by mitsubishi chemical company; "630", "630LSD", "604" (glycidyl amine type epoxy resin) manufactured by Mitsubishi chemical corporation; "ED-523T" (glycine ring epoxy resin) manufactured by ADEKA company; "EP-3950L", "EP-3980S" (glycidyl amine type epoxy resins) manufactured by ADEKA Co; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co., ltd; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nissan chemical materials Co., ltd. (NIPPON STEEL Chemical & Material Co.); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daxil corporation; "PB-3600" by Daxillon corporation, and "JP-100" and "JP-200" by Japan, respectively (epoxy resin having butadiene structure); "ZX1658" and "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nissan chemical materials Co., ltd. They may be used alone or in combination of 1 or more than 2.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
As the solid epoxy resin, there are preferable a binaphthol-type epoxy resin, a naphthalene-type tetrafunctional epoxy resin, a naphthol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol-type epoxy resin, a biphenyl-type epoxy resin, a naphthylene ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol a-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenyl ethane-type epoxy resin, and a phenol benzopyrrolone-type epoxy resin.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC corporation; "HP-4700", "HP-4710" manufactured by DIC corporation (naphthalene type tetrafunctional epoxy resin); "N-690" (cresol novolac type epoxy resin) manufactured by DIC Co., ltd; "N-695" manufactured by DIC Co., ltd. (cresol novolak type epoxy resin); "HP-7200", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene type epoxy resin) manufactured by DIC Co; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) manufactured by DIC Co., ltd; "EPPN-502H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd; "NC7000L" manufactured by Japanese chemical Co., ltd. (naphthol novolac type epoxy resin); "NC3000H", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by japan chemical pharmaceutical company; "ESN475V" and "ESN4100V" manufactured by Nissan chemical materials Co., ltd. (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "ESN375" manufactured by Nissan chemical materials Co., ltd. (dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000HK", "YL7890" (Bixylenol type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi chemical corporation; "YX8800" (anthracene-type epoxy resin) manufactured by mitsubishi chemical company; "YX7700" manufactured by Mitsubishi chemical corporation (phenol aralkyl type epoxy resin); "PG-100", "CG-500" manufactured by Osaka gas chemical Co., ltd; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi chemical corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi chemical corporation; "jER1010" (bisphenol a type epoxy resin) manufactured by mitsubishi chemical company; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by mitsubishi chemical company; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Japanese chemical Co., ltd. They may be used alone or in combination of 1 or more than 2.
As the (a) epoxy resin, in the case of using a liquid epoxy resin and a solid epoxy resin in combination, the mass ratio thereof (liquid epoxy resin: solid epoxy resin) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, particularly preferably 7:1 to 1:7.
(A) The epoxy group equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 3,000g/eq, still more preferably 80g/eq to 2,000g/eq, and particularly preferably 110g/eq to 1,000g/eq. Epoxy equivalent means the mass of the resin per 1 equivalent of epoxy. The epoxy group equivalent can be measured in accordance with JIS K7236.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by Gel Permeation Chromatography (GPC) as a value in terms of polystyrene.
The content of the (a) epoxy resin in the resin composition is preferably 1 mass% or more, more preferably 2 mass% or more, particularly preferably 4 mass% or more, preferably 25 mass% or less, more preferably 20 mass% or less, particularly preferably 10 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. (A) When the amount of the epoxy resin is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved. The plating peel strength indicates a force required to peel the plated conductor layer, unless otherwise specified, when the plated conductor layer is formed on the insulating layer formed of the cured product of the resin composition. The higher the plating peel strength, the more excellent the adhesion between the insulating layer and the plated conductor layer.
The content of the epoxy resin (a) in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 20 mass% or more, preferably 70 mass% or less, more preferably 60 mass% or less, particularly preferably 50 mass% or less, based on 100 mass% of the resin component in the resin composition. The resin component of the resin composition means a component other than the inorganic filler (D) in the nonvolatile component of the resin composition. (A) When the amount of the epoxy resin is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
[ (B) curing agent ]
The resin composition according to one embodiment of the present invention contains a (B) curing agent as a (B) component. The curing agent (B) does not contain any substance belonging to the component (A). (B) The curing agent may have a function of curing the (a) epoxy resin. (B) The curing agent may be used alone or in combination of 1 or more than 2.
(B) The curing agent preferably contains (B-1) an active ester-based curing agent. (B) When the curing agent contains (B-1) an active ester-based curing agent, the dielectric loss tangent of the cured product of the resin composition can be effectively reduced. The active ester-based curing agent (B-1) may be used alone or in combination of 1 or more than 2.
As the (B-1) active ester curing agent, compounds having 2 or more ester groups having high reactivity in 1 molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, and the like, can be generally preferably used. The active ester-based curing agent is preferably a product obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound (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 Phenolic compound (phenol compound) or naphthol compound include hydroquinone, resorcinol, 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, phloroglucinol, dicyclopentadiene type diphenol compound, novolac (Phenolic Novolac) and the like. The "dicyclopentadiene type phenol compound" herein means a phenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.
Specifically, as the (B-1) active ester-based curing agent, a dicyclopentadiene-type active ester-based curing agent, a naphthalene-type active ester-based curing agent containing a naphthalene structure, an active ester-based curing agent containing an acetylation product of a novolac resin, and an active ester-based curing agent containing a benzoyl product of a novolac resin are preferable, and among these, at least 1 selected from the dicyclopentadiene-type active ester-based curing agent and the naphthalene-type active ester-based curing agent is more preferable, and a naphthalene-type active ester-based curing agent is particularly preferable. The dicyclopentadiene type active ester-based curing agent preferably contains an active ester-based curing agent having a dicyclopentadiene type diphenol structure.
As the commercial product of the (B-1) active ester-based curing agent, for example, as the active ester-based curing agent containing a dicyclopentadiene-type diphenol structure, "EXB9451", "EXB9460S", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC Co.); examples of the active ester-based curing agent having a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T", and "EXB-8" (manufactured by DIC Co.); examples of the phosphorus-containing active ester curing agent include "EXB9401" (manufactured by DIC Co., ltd.); examples of the active ester-based curing agent which is an acetylation product of a novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester-based curing agent which is a benzoyl compound of the novolac resin include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester-based curing agent having a styrene group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Air Water Co., ltd.).
When the number of epoxy groups of the epoxy resin (a) is 1, the number of active ester groups of the (B-1) active ester curing agent is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1 or more, preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less. The "epoxy number of the epoxy resin (a)" means a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of the epoxy resin (a) existing in the resin composition by the epoxy equivalent weight. The term "(number of active ester groups of B-1) active ester-based curing agent" means a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of the (B-1) active ester-based curing agent present in the resin composition by the equivalent weight of the active ester groups.
The content of the (B-1) active ester-based curing agent in the resin composition is preferably 1 mass% or more, more preferably 5 mass% or more, particularly preferably 10 mass% or more, preferably 40 mass% or less, more preferably 30 mass% or less, particularly preferably 20 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. When the amount of the active ester-based curing agent (B-1) is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
The content of the (B-1) active ester curing agent in the resin composition is preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 30 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, particularly preferably 60 mass% or less, based on 100 mass% of the resin component in the resin composition. When the amount of the active ester-based curing agent (B-1) is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
The mass ratio of the (B-1) active ester-based curing agent to the (C) silicon-containing resin in the resin composition ((B-1) active ester-based curing agent/(C) silicon-containing resin) is preferably within a specific range. Specifically, the mass ratio ((B-1) active ester-based curing agent/(C) silicon-containing resin) is preferably 0.1 or more, more preferably 1 or more, particularly preferably 2 or more, preferably 100 or less, more preferably 50 or less, particularly preferably 30 or less. When the mass ratio ((B-1) active ester-based curing agent/(C) silicon-containing resin) falls within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
Examples of the curing agents other than the (B-1) active ester curing agent include phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate curing agents, and thiol curing agents. These curing agents may be used alone or in combination of 1 or more than 2. Among them, a phenol-based curing agent and a carbodiimide-based curing agent are preferable.
As the phenolic curing agent, a curing agent having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule can be used. From the viewpoints of heat resistance and water resistance, a phenol curing agent having a phenol structure (novolac structure) is preferable. In addition, from the viewpoint of adhesion, a nitrogen-containing phenol-based curing agent is preferable, and a phenol-based curing agent containing a triazine skeleton is more preferable. Among them, a novolac resin (Phenolic Novolac Resin) containing a triazine skeleton is preferable from the viewpoint of improving heat resistance, water resistance and adhesion. Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals, and "NHN", "CBN", "GPH" manufactured by Japanese chemical Co., ltd., and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395", and "LA-7052", "LA-7054", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by DIC.
As the carbodiimide-based curing agent, a curing agent having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule can be used. Specific examples of the carbodiimide-based curing agent include: aliphatic dicarboximides such as tetramethylene-bis (t-butylcarbodiimide), and cyclohexanedis (methylene-t-butylcarbodiimide); aromatic dicarboximides such as phenylene-bis (xylyl carbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexyl carbodiimide) and poly (isophorone carbodiimide); and aromatic polycarbodiimides such as poly (phenylene carbodiimides), poly (naphthylene carbodiimides), poly (tolylene carbodiimides), poly (methyldiisopropylphenylene carbodiimides), poly (triethylphenylene carbodiimides), poly (diethylphenylene carbodiimides), poly (triisopropylphenylene carbodiimides), poly (diisopropylphenylene carbodiimides), poly (xylylene carbodiimides), poly (tetramethylxylylene carbodiimides), poly (methylenediphenylene carbodiimides), poly [ methylenebis (methylphenyl) carbodiimides ]. Specific examples of the carbodiimide-based curing agent include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nikko chemical Co., ltd; "Stabaxol P", "Stabaxol P400", "Hycasyl 510" and the like manufactured by Rhein Chemie, inc.
The acid anhydride-based curing agent may be a curing agent having 1 or more acid anhydride groups in 1 molecule, and preferably a curing agent having 2 or more acid anhydride groups in 1 molecule. Specific examples of the acid anhydride-based curing agent include: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenyl sulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (dehydrated trimellitate), styrene-maleic anhydride copolymerized from styrene and maleic acid, and the like. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by New Japan physical and chemical Co., ltd; "YH-306", "YH-307" manufactured by Mitsubishi chemical corporation; "HN-2200", "HN-5500" manufactured by Hitachi chemical Co., ltd; gram Lei Weili (Cray Valley) company "EF-30", "EF-40", "EF-60", "EF-80", etc.
As the amine-based curing agent, a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule can be used. Examples of the amine-based curing agent include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferable. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine-based curing agent include: 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine 4,4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Examples of the commercial products of the amine-based curing agent include "SEIKACURE-S" manufactured by SEIKA corporation; "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Kayabond Corp; "EPICURE W" manufactured by Mitsubishi chemical corporation; "DTDA" manufactured by Sumitomo refinement Co., ltd.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE chemical Co., ltd; "HFB2006M" manufactured by Showa Polymer Co., ltd., and "P-d" and "F-a" manufactured by Sichuang chemical industry Co., ltd.
Examples of the cyanate-based curing agent include: difunctional cyanate resins such as bisphenol a dicyanate, polyphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate-based) phenylpropane, 1-bis (4-cyanate-based phenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanate-phenyl-1- (methylethylene)) benzene, bis (4-cyanate-phenyl) sulfide, and bis (4-cyanate-based phenyl) ether; polyfunctional cyanate resins derived from phenol novolac resins, cresol novolac resins, and the like; prepolymers obtained by triazinizing a part of these cyanate resins, and the like. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by Lonza Japan (both of which are phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers obtained by triazining a part or all of bisphenol a dicyanate to form a trimer).
Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
(B) The active group equivalent of the curing agent is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, still more preferably 100g/eq to 500g/eq, particularly preferably 100g/eq to 300g/eq. The active group equivalent means the mass of the curing agent per 1 equivalent of active group.
When the number of epoxy groups of the epoxy resin (a) is 1, the number of active groups of the curing agent (B) is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1 or more, preferably 10 or less, more preferably 5 or less, and particularly preferably 2 or less. The "active base number of the curing agent" (B) means a value obtained by adding all the values obtained by dividing the mass of the nonvolatile component of the curing agent (B) existing in the resin composition by the active base equivalent weight.
The content of the curing agent (B) in the resin composition is preferably 3 mass% or more, more preferably 5 mass% or more, further preferably 8 mass% or more, particularly preferably 10 mass% or more, preferably 40 mass% or less, more preferably 30 mass% or less, further preferably 20 mass% or less, and particularly preferably 18 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. (B) When the amount of the curing agent is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
The content of the curing agent (B) in the resin composition is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 20 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, particularly preferably 60 mass% or less, based on 100 mass% of the resin component in the resin composition. (B) When the amount of the curing agent is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
[ (C) silicon-containing resin (alkoxysilyl group-containing and hydrogenated conjugated diene-aromatic vinyl copolymer resin) ]
The resin composition according to one embodiment of the present invention contains, as the component (C), a silicon-containing resin (i.e., (C) an alkoxysilyl group-containing and hydrogenated conjugated diene-aromatic vinyl copolymer resin).
The conjugated diene-aromatic vinyl copolymer resin means a resin having a structure obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. The alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin means a resin having a structure in which an alkoxysilyl group is introduced into a resin having a structure obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound. Further, (C) the alkoxysilyl group-containing and hydrogenated conjugated diene-aromatic vinyl copolymer resin (i.e., the (C) silicon-containing resin) includes any of "alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin" and "resin having a structure in which carbon-carbon unsaturated bonds of the alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin are hydrogenated". However, the method for producing the silicon-containing resin (C) is not limited. Therefore, (C) the silicon-containing resin can be produced by a method other than the method of copolymerizing a conjugated diene compound and an aromatic vinyl compound, introducing an alkoxysilyl group, and if necessary, hydrogenating the resultant product.
(C) The silicon-containing resin generally contains (c 1) conjugated diene compound units which can be hydrogenated. The conjugated diene compound unit (c 1) which may be hydrogenated may have an alkoxysilyl group bonded thereto. Hereinafter, the conjugated diene compound unit (c 1) which can be hydrogenated is sometimes referred to as "(c 1) diene unit".
The conjugated diene compound unit means a structural unit having a structure formed by polymerizing a conjugated diene compound. However, the method for producing the conjugated diene compound unit is not limited. Accordingly, the conjugated diene compound units may also be formed by a method other than polymerization of the conjugated diene compound.
The conjugated diene compound unit that can be hydrogenated includes any of conjugated diene compound units, and hydrogenated conjugated diene compound units. The hydrogenated conjugated diene compound unit means a structural unit having a structure in which a part or all of the carbon-carbon unsaturated bonds of the conjugated diene compound unit are hydrogenated. However, the method for producing the hydrogenated conjugated diene compound unit is not limited. Thus, the hydrogenated conjugated diene compound units may also be formed by a method other than hydrogenation of the carbon-carbon unsaturated bonds of the conjugated diene compound units.
As the conjugated diene compound corresponding to the conjugated diene compound unit, a diene compound having a carbon atom chain containing 4 carbon atoms bonded in this order of double bond, single bond, and double bond can be used. Examples of the conjugated diene compound include butadiene, isoprene, dimethylbutadiene, 1, 3-pentadiene, and 3-methyl-1, 3-pentadiene. The conjugated diene compound may be used alone or in combination of 1 or more than 2. Therefore, 1 kind of (c 1) diene unit may be used alone, or 2 or more kinds may be used in combination.
Among the conjugated diene compounds, butadiene is preferable. Therefore, as the (c 1) diene unit, a butadiene unit which can be hydrogenated is preferable. The butadiene unit means a structural unit having a structure formed by polymerizing butadiene. In addition, the butadiene unit which can be hydrogenated includes any of a butadiene unit and a hydrogenated butadiene unit. The hydrogenated butadiene unit is a structural unit having a structure in which a part or all of carbon-carbon unsaturated bonds of the butadiene unit are hydrogenated. However, the method for producing butadiene units which can be hydrogenated is not limited.
The amount of the diene unit (C1) is preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 30 mass% or more, preferably 70 mass% or less, more preferably 60 mass% or less, particularly preferably 50 mass% or less, based on 100 mass% of the silicon-containing resin (C). The amount of the (c 1) diene unit includes both an alkoxysilyl group-bonded (c 1) diene unit and an alkoxysilyl group-unbonded (c 1) diene unit.
It is preferable that an alkoxysilyl group is bonded to a part or all of the diene units (c 1). In this case, the alkoxysilyl group is preferably bonded to at least the direct addition unit in the diene unit (c 1). This will be described in detail below.
Conjugated diene compounds generally have a carbon atom chain containing 4 carbon atoms bonded (bonded) in this order by a double bond, a single bond, and a double bond. The aforementioned carbon atom chain has the same carbon skeleton as that of 1, 3-butadiene, and therefore, may be hereinafter referred to as "butadiene carbon skeleton".
When the conjugated diene compound is polymerized, a conjugated addition reaction and a direct addition reaction can usually occur. In the conjugated addition reaction, 1,4 addition reaction in which carbon atoms at 1 and 4 positions of the butadiene carbon skeleton are bonded occurs. Accordingly, the conjugated diene compound units produced by the conjugated addition reaction contain a double bond in the main chain connecting carbon atoms bonded to other structural units to each other. The conjugated diene compound unit containing a double bond in the main chain as such generally contains the same carbon atom chain as that of 1, 4-polybutadiene. In the following, among the diene units (c 1), a conjugated diene compound unit having a double bond in the main chain and a structural unit having a structure in which a carbon-carbon unsaturated bond thereof is hydrogenated may be referred to as a "conjugated addition unit".
On the other hand, in the direct addition reaction, 1,2 addition reactions in which carbon atoms at the 1-and 2-positions of the butadiene carbon skeleton are bonded occur. Therefore, the conjugated diene compound units produced by the direct addition reaction contain no double bond in the main chain, but contain a double bond in the side chain. The conjugated diene compound unit containing a double bond in the side chain as such usually contains the same carbon atom chain as that of 1, 2-polybutadiene. In the following, among the diene units (c 1), a conjugated diene compound unit having a double bond in a side chain and a structural unit having a structure in which a carbon-carbon unsaturated bond thereof is hydrogenated may be referred to as a "direct addition unit".
Therefore, the silicon-containing resin (C) may contain a conjugated addition unit and a direct addition unit as the diene unit (C1). In the case where an alkoxysilyl group is bonded to the diene unit (c 1), it is preferable that an alkoxysilyl group is bonded to at least the direct addition unit. In this case, the alkoxysilyl group is preferably bonded to a side chain of the direct addition unit. In addition, an alkoxysilyl group may be bonded to a part of the direct addition units contained in the silicon-containing resin (C), but an alkoxysilyl group is more preferably bonded to all the direct addition units. When an alkoxysilyl group is bonded to the direct addition unit, the dielectric loss tangent of the cured product of the resin composition can be effectively reduced, and crack resistance can be effectively improved.
In the case where an alkoxysilyl group is bonded to the (c 1) diene unit, the alkoxysilyl group may be directly bonded to the (c 1) diene unit or may be indirectly bonded to the (c 1) diene unit via a divalent linking group. Examples of the "divalent linking group" include an optionally substituted divalent hydrocarbon group such as an optionally substituted alkylene group, an optionally substituted alkenylene group, an optionally substituted alkynylene group, an optionally substituted arylene group, and the like; -a group represented by C (=o) O, -a group represented by C (=o) NH, -a group represented by NHC (=o) O, -a group represented by S, -a group represented by SO, -a group represented by NH-, a group formed by combining a plurality of these groups, and the like. Examples of the substituent include a halogen atom, a cycloalkyloxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a silyl group, an acyl group, an acyloxy group, a carboxyl group, a sulfo group, a cyano group, a nitro group, a hydroxyl group, a mercapto group, an oxo group, and the like. The divalent linking group is preferably a divalent hydrocarbon group optionally having a substituent, and more preferably a divalent hydrocarbon group not having a substituent. Among them, the alkoxysilyl group is preferably directly bonded to the (c 1) diene unit.
(C) The silicon-containing resin generally comprises (c 2) an aromatic vinyl compound unit. The (c 2) aromatic vinyl compound unit means a structural unit having a structure formed by polymerizing an aromatic vinyl compound. However, the method for producing the aromatic vinyl compound unit (c 2) is not limited. Therefore, the (c 2) aromatic vinyl compound unit may be formed by a method other than polymerization of the aromatic vinyl compound.
As the aromatic vinyl compound corresponding to the aromatic vinyl compound unit (c 2), a compound containing an aromatic ring and an optionally substituted vinyl group bonded to the aromatic ring can be used. Examples of the aromatic vinyl compound include styrene, vinyltoluene, ethylstyrene, vinylnaphthalene, 4-t-butylstyrene, 4-acetoxystyrene, 4-vinylphenol, 4-t-butoxystyrene, 1- (1-ethoxyethoxy) -4-vinylbenzene, and 9-vinylanthracene. The aromatic vinyl compound may be used alone or in combination of 1 or more than 2. Therefore, 1 or 2 or more aromatic vinyl compound units may be used alone or in combination.
Among the aromatic vinyl compounds, styrene is preferable. Therefore, as the (c 2) aromatic vinyl compound unit, a styrene unit is preferable. The styrene unit means a structural unit having a structure formed by polymerizing styrene. However, the method for producing the styrene unit is not limited.
The amount of the aromatic vinyl compound unit (C2) is preferably 15 mass% or more, more preferably 18 mass% or more, particularly preferably 20 mass% or more, preferably 60 mass% or less, more preferably 50 mass% or less, particularly preferably 40 mass% or less, based on 100 mass% of the silicon-containing resin (C).
(C) In the silicon-containing resin, the mass ratio of (c 1) diene units to (c 2) aromatic vinyl compound units ((c 1) diene units/(c 2) aromatic vinyl compound units) is preferably within a specific range. Here, the mass of the (c 1) diene unit includes both the mass of the (c 1) diene unit having an alkoxysilyl group bonded thereto and the mass of the (c 1) diene unit not having an alkoxysilyl group bonded thereto. The mass ratio ((c 1) diene unit/(c 2) aromatic vinyl compound unit) is preferably 0.1 or more, more preferably 0.5 or more, particularly preferably 1 or more, preferably 100 or less, more preferably 10 or less, particularly preferably 5 or less.
(C) The silicon-containing resin may contain (c 3) alkenylalkoxysilane units. The (c 3) alkenylalkoxysilane unit means a structural unit having a structure formed by polymerizing an alkenylalkoxysilane compound. The alkenylalkoxysilane compound means a compound containing a Si atom, 1 or more alkenyl groups bonded to the Si atom, and 1 or more alkoxy groups bonded to the Si atom.
Since the alkenyl alkoxysilane compound can polymerize by reaction of the carbon-carbon double bond contained in the alkenyl group, (C3) alkenylalkoxysilane units as repeating units of (C) the silicon-containing resin can be formed. Further, the (c 3) alkenylalkoxysilane unit may contain an alkoxysilyl group derived from an alkenylalkoxysilane compound. However, the method for producing the (c 3) alkenylalkoxysilane unit is not limited. Thus, (c 3) the alkenylalkoxysilane unit may also be formed by a method other than polymerizing the alkenylalkoxysilane compound.
Examples of the alkenylalkoxysilane compound corresponding to the alkenylalkoxysilane unit (c 3) include vinyltrimethoxysilane, vinyltriethoxysilane, and octenyltrimethoxysilane. The alkenylalkoxysilane compound may be used alone in an amount of 1 or in an amount of 2 or more. Therefore, 1 kind of (c 3) alkenylalkoxysilane unit may be used alone, or 2 or more kinds may be combined.
(c3) The alkenylalkoxysilane unit may include a unit having the same structure as the (c 1) diene unit to which the alkoxysilyl group is bonded. In the present specification, among the structural units contained in the (C) silicon-containing resin, structural units that may belong to both (C1) diene units and (C3) alkenylalkoxysilane units that are bonded to alkoxysilyl groups are classified as (C1) diene units that are bonded to alkoxysilyl groups.
The amount of the alkenylalkoxysilane unit (C3) may be 0 mass% or more and preferably 10 mass% or more, more preferably 20 mass% or more, particularly preferably 30 mass% or more, preferably 70 mass% or less, more preferably 60 mass% or less, and particularly preferably 50 mass% or less, based on 100 mass% of the silicon-containing resin (C).
The silicon-containing resin (C) may further contain an optional structural unit in addition to the diene unit (C1), the aromatic vinyl compound unit (C2), and the alkenylalkoxysilane unit (C3). However, (C) the silicon-containing resin preferably does not contain optional structural units.
The silicon-containing resin (C) is particularly preferably a resin having a structure represented by the following formula (1). Therefore, (C) the silicon-containing resin preferably contains a resin containing a structure represented by the following formula (1), and more preferably contains only a resin containing a structure represented by the following formula (1).
[ chemical formula 3]
(in the formula (1),
R 1 ～R 31 、R 34 ～R 40 and R is 43 ～R 45 Each independently represents a hydrogen atom, or a monovalent hydrocarbon group,
x represents a single bond or a divalent linking group,
R 32 、R 33 、R 41 r is R 42 Each independently represents a monovalent hydrocarbon group,
ar represents an aryl group optionally having a substituent,
a. b, c and d each independently represent an integer of 0 or more,
e and f represent integers of 0 or more satisfying e+f 1 or more,
g represents an integer of 1 or more,
h and i each independently represent an integer of 1 to 3, and the order of the repeating units a, b, c, d, e, f, and g is arbitrary. ).
In the formula (1), R 1 ～R 31 、R 34 ～R 40 And R is 43 ～R 45 Each independently represents a hydrogen atom, or a monovalent hydrocarbon group. The monovalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon groupBut is preferably an aliphatic hydrocarbon group. The aliphatic hydrocarbon group is typically a saturated aliphatic hydrocarbon group. The monovalent hydrocarbon group may be a linear or branched hydrocarbon group or a cyclic hydrocarbon group. The number of carbon atoms of the monovalent hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 6. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; aryl groups such as phenyl, α -naphthyl, β -naphthyl, and the like. Wherein R is 1 ～R 31 、R 34 ～R 40 And R is 43 ～R 45 Each independently is preferably a hydrogen atom or an alkyl group, and particularly preferably a hydrogen atom.
In formula (1), X represents a single bond or a divalent linking group. As "divalent linking group", a divalent linking group as described above may be used. Among them, as the divalent linking group, an optionally substituted alkylene group, an optionally substituted alkenylene group, an optionally substituted alkynylene group, an optionally substituted arylene group or the like, and an optionally substituted divalent hydrocarbon group is preferable. The number of carbon atoms of the divalent hydrocarbon group is usually 1 or more, preferably 2 or more, preferably 20 or less, more preferably 12 or less, further preferably 10 or less, further preferably 8 or less, and particularly preferably 6 or less. The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group may be any of straight chain, branched, and cyclic. Examples of such alkylene groups include methylene, ethylene, propylene, butylene, pentylene, hexylene, and 1, 1-dimethylethylene, and the like, and methylene, ethylene, and 1, 1-dimethylethylene are preferred, and ethylene is particularly preferred. The alkenylene group is preferably an alkenylene group having 2 to 10 carbon atoms, more preferably an alkenylene group having 2 to 6 carbon atoms, and still more preferably an alkenylene group having 2 to 5 carbon atoms. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and more preferably an arylene group having 6 to 10 carbon atoms. Among them, X is preferably a divalent alkylene group optionally having a substituent, and more preferably a divalent alkylene group not having a substituent.
In the formula (1), R 32 、R 33 、R 41 And R is 42 Each independently represents a monovalent hydrocarbon group. R is R 32 、R 33 、R 41 And R is 42 The monovalent hydrocarbon radicals represented may be those represented by R 1 ～R 31 、R 34 ～R 40 And R is 43 ～R 45 Monovalent hydrocarbon groups of the same range as the monovalent hydrocarbon groups represented. As R 32 、R 33 、R 41 And R is 42 Alkyl and aryl groups are preferred, alkyl groups are more preferred, straight-chain alkyl groups are even more preferred, and methyl and ethyl groups are particularly preferred.
In the formula (1), ar represents an aryl group optionally having a substituent. The number of carbon atoms of the aryl group is preferably 6 or more, more preferably 14 or less, and still more preferably 10 or less. Examples of the aryl group include phenyl, naphthyl, and anthracenyl. Examples of the substituent that the aryl group may have include halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and iodine atoms; monovalent hydrocarbon groups such as alkyl, aryl, and arylalkyl; cycloalkyloxy, aryloxy, arylalkoxy, monovalent heterocyclic groups, amino, silyl, acyl, acyloxy, carboxyl, sulfo, cyano, nitro, hydroxy, mercapto, and the like. Among them, the substituent is preferably a monovalent hydrocarbon group, more preferably an alkyl group and an aryl group, and further preferably an alkyl group. In particular, ar is preferably an unsubstituted aryl group.
In the formula (1), a, b, c and d each independently represent an integer of 0 or more. Specifically, a and b are each independently usually 0 or more, preferably 1 or more, more preferably 2 or more, preferably 300 or less, more preferably 200 or less. The values of c and d are usually 0 or more, but may be 1 or more, and are preferably 200 or less, more preferably 100 or less.
In the formula (1), e and f represent integers of 0 or more satisfying e+f.gtoreq.1, and particularly, e is preferably 1 or more. Specifically, e is usually 0 or more, preferably 1 or more, more preferably 2 or more, preferably 200 or less, more preferably 100 or less. In addition, f is usually 0 or more, may be 1 or more, and is preferably 100 or less. In addition, e+f preferably satisfies 0.02.ltoreq.e+f)/(a+b+c+d+e+f+g) < 1.0.
In the formula (1), g represents an integer of 1 or more. Specifically, g is usually 1 or more, preferably 2 or more, preferably 300 or less, more preferably 200 or less, and particularly preferably 100 or less.
In the formula (1), the order of the repeating units a, b, c, d, e, f, and g is arbitrary.
In the formula (1), h and i each independently represent an integer of 1 to 3, preferably 2 to 3, and more preferably 3.
A more preferable specific example of the silicon-containing resin (C) is a resin having a structure represented by the following formula (2).
[ chemical formula 4]
(in the formula (2),
y represents a single bond or a divalent hydrocarbon group,
R 46 r is R 47 Each independently represents a monovalent hydrocarbon group,
j and k each independently represent an integer of 0 or more,
l and m each independently represent an integer greater than 0,
n represents an integer of 1 to 3,
the order of the repeating units j, k, l, and m is arbitrary. ).
In the formula (2), Y represents a single bond or a divalent hydrocarbon group. The divalent hydrocarbon group represented by Y may be the same range of the divalent hydrocarbon group represented by X of the formula (1). Y is preferably a divalent hydrocarbon group, more preferably an alkylene group, particularly preferably an ethylene group.
In the formula (2), R 46 R is R 47 Each independently represents a monovalent hydrocarbon group. R is R 46 R is R 47 Can be in the range of R as described above 32 、R 33 、R 41 And R is 42 The same applies.
In the formula (2), j and k each independently represent an integer of 0 or more. Specifically, j represents an integer having the same range as a and b in the formula (1). K represents an integer having the same range as c and d in the formula (1).
In formula (2), l and m each independently represent an integer greater than 0. Specifically, l represents an integer having the same range as e in formula (1). In addition, l preferably satisfies 0.02.ltoreq.l/(j+k+l+m) < 1.0. In addition, m represents an integer in the same range as g of formula (1).
In the formula (2), the order of the repeating unit j, the repeating unit k, the repeating unit l, and the repeating unit m is arbitrary.
In the formula (2), n represents an integer of 1 to 3, preferably 2 to 3, more preferably 3.
In particular, the amount of the alkoxysilyl group-containing unit (repeating unit e, repeating unit f, repeating unit l, etc. described above) is preferably 3% or more based on 100% by mass of the silicon-containing resin (C).
(C) The method for producing the silicon-containing resin is not limited. (C) The silicon-containing resin can be produced, for example, by a method comprising: a conjugated diene-aromatic vinyl copolymer such as butadiene-styrene copolymer is reacted with an alkoxysilane compound such as trimethoxysilane, methyldimethoxysilane, dimethylmethoxysilane, triethoxysilane, methyldiethoxysilane, dimethylethoxysilane, etc. in the presence of a catalyst containing a platinum compound, to thereby obtain an alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin. For this production method, for example, refer to Japanese patent application laid-open No. 2017-8301. In addition, (C) the silicon-containing resin can be produced, for example, by a method comprising: the alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin is obtained by copolymerizing a conjugated diene compound and an aromatic vinyl compound with an alkenylalkoxysilane compound. Further, the method for producing the (C) silicon-containing resin may include: after the alkoxysilyl group-containing conjugated diene-aromatic vinyl copolymer resin is obtained, the resin is hydrogenated.
As the silicon-containing resin (C), commercially available ones can be used. Examples of the commercial products of the silicon-containing resin (C) include "X-12-1281C" and "X-12-1281A" manufactured by Xinyue chemical industry Co., ltd. (resin in which trimethoxysilyl group is introduced into a side chain of a direct addition unit of a styrene-butadiene copolymer); "X-12-1281A-ES" manufactured by Xinyue chemical industry Co., ltd. (resin in which triethoxysilyl groups are introduced into side chains of direct addition units of a styrene-butadiene copolymer) and the like.
(C) The silicon-containing resin may be used alone in an amount of 1 or in an amount of 2 or more.
(C) The number average molecular weight of the silicon-containing resin is preferably 2,000 or more, more preferably 3,000 or more, particularly preferably 4,000 or more, preferably 40,000 or less, more preferably 35,000 or less, particularly preferably 30,000 or less. The number average molecular weight can be measured by Gel Permeation Chromatography (GPC) as a value in terms of polystyrene.
The content of the silicon-containing resin (C) in the resin composition is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 0.2 mass% or more, preferably 10 mass% or less, more preferably 6 mass% or less, and particularly preferably 4 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. (C) When the amount of the silicon-containing resin is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
The content of the silicon-containing resin (C) in the resin composition is preferably 0.5 mass% or more, more preferably 1 mass% or more, particularly preferably 2 mass% or more, preferably 15 mass% or less, more preferably 10 mass% or less, particularly preferably 8 mass% or less, based on 100 mass% of the resin component in the resin composition. (C) When the amount of the silicon-containing resin is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
[ (D) inorganic filler ]
The resin composition according to one embodiment of the present invention may further contain (D) an inorganic filler as an optional component in addition to the above-described components (a) to (C). The (D) inorganic filler as the (D) component is generally contained in the resin composition in the form of particles. When the inorganic filler (D) is used, the dielectric loss tangent of the cured product of the resin composition can be effectively reduced.
As the material of the inorganic filler (D), an inorganic compound is used. Examples of the material of the inorganic filler (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium 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, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among these, silica and alumina are preferable, and silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as silica. (D) The inorganic filler may be used alone or in combination of at least 2 kinds.
Examples of the commercial products of the inorganic filler (D) include "SP60-05" and "SP507-05" manufactured by Nissan chemical materials Co., ltd; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C-MJE", "YA010C" manufactured by Admatechs; "UFP-30", "DAW-03", "FB-105FD", manufactured by DENKA Co., ltd; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "CellSpheres" manufactured by Taiheiyo-ceramic company; and "eyebox" manufactured by solar volatile catalyst formation company.
The average particle diameter of the inorganic filler (D) is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, particularly preferably 0.2 μm or more, preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, and particularly preferably 1 μm or less, from the viewpoint of significantly obtaining the desired effect of the present invention.
(D) The average particle size of the inorganic filler material can be determined using a laser diffraction-scattering method based on Mie scattering theory. Specifically, the measurement can be performed by: the particle size distribution of the inorganic filler was prepared based on volume by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size was used as the average particle size. As a measurement sample, a product obtained by weighing 100mg of an inorganic filler, 10g of methyl ethyl ketone into a vial, and dispersing the mixture by ultrasonic waves for 10 minutes was used. For the measurement sample, a laser diffraction type particle size distribution measuring apparatus was used, the wavelength of the light source was set to blue and red, the volume-based particle size distribution of the inorganic filler was measured by a flow cell (flow cell) method, and the average particle size as the median particle size was calculated from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
The specific surface area of the inorganic filler (D) is preferably 0.1m from the viewpoint of significantly obtaining the desired effect of the present invention 2 Preferably at least 0.5m 2 Preferably 1m or more, and more preferably 1m 2 Preferably 3m or more per gram 2 Preferably 100m or more per gram 2 Preferably less than or equal to/g, more preferably 70m 2 Preferably 50m or less per gram 2 Preferably less than or equal to/g, particularly preferably 40m 2 And/g or less. The specific surface area of the inorganic filler material can be determined by: the specific surface area was calculated by the BET multipoint method by adsorbing nitrogen gas on the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by mountain Co., ltd.) according to the BET method.
The inorganic filler (D) is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treating agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilane compounds, titanate coupling agents, and the like. The surface treating agent may be used alone or in combination of 1 or more than 2.
Examples of the commercial products of the surface treatment agent include "KBM403" (3-glycidoxypropyl trimethoxysilane), "KBM803" (3-mercaptopropyl trimethoxysilane), "KBE903" (3-aminopropyl triethoxysilane), "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" (hexamethyldisilazane), "KBM103" (phenyl trimethoxysilane), and "KBM-4803" (long chain epoxy silane coupling agent), and "KBM-7103" (3, 3-trifluoropropyl trimethoxysilane) manufactured by Xinshi chemical industries, etc.
From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably controlled to a specific range. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface-treating agent, more preferably 0.2 to 3 mass% of a surface-treating agent, and even more preferably 0.3 to 2 mass% of a surface-treating agent, based on 100 mass% of the inorganic filler.
The degree of surface treatment based on the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving dispersibility of the inorganic filler 2 The above is more preferably 0.1mg/m 2 The above is more preferably 0.2mg/m 2 The above. On the other hand, from the viewpoint of preventing an increase in melt viscosity of the resin composition, the carbon amount per unit surface area of the inorganic filler is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 Hereinafter, it is more preferably 0.5mg/m 2 The following is given.
(D) The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is subjected to a washing treatment with a solvent (e.g., methyl Ethyl Ketone (MEK)). Specifically, MEK as a solvent in a sufficient amount may be added to the inorganic filler surface-treated with the surface treating agent, and ultrasonic washing may be performed at 25 ℃ for 5 minutes. The supernatant was removed, and the solid content was dried, and then the carbon content per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
The content of the inorganic filler (D) in the resin composition may be 0 mass% or more, preferably 50 mass% or more, more preferably 60 mass% or more, particularly preferably 70 mass% or more, preferably 90 mass% or less, more preferably 86 mass% or less, and particularly preferably 82 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. (D) When the amount of the inorganic filler is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
The mass ratio of (D) the inorganic filler to (C) the silicon-containing resin in the resin composition ((D) the inorganic filler/(C) the silicon-containing resin) is preferably within a specific range. Specifically, the mass ratio ((D) inorganic filler/(C) silicon-containing resin) is preferably 5 or more, more preferably 10 or more, particularly preferably 20 or more, preferably 300 or less, more preferably 200 or less, particularly preferably 150 or less. When the mass ratio ((D) inorganic filler/(C) silicon-containing resin) is within the above range, the dielectric loss tangent and crack resistance of the cured product of the resin composition can be particularly improved, and further, the plating peel strength can be generally effectively improved.
[ (E) thermoplastic resin ]
The resin composition according to one embodiment of the present invention may further contain (E) a thermoplastic resin as an optional component in addition to the above-described components (a) to (D). The thermoplastic resin (E) as the component (E) does not contain any component (A) to (D).
Examples of the thermoplastic resin (E) include phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene oxide resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. (E) The thermoplastic resin may be used alone or in combination of 1 or more than 2.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from the group consisting of bisphenol a skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenol skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group of a phenolic hydroxyl group, an epoxy group, and the like.
Specific examples of the phenoxy resin include "1256" and "4250" manufactured by mitsubishi chemical company (all of which are phenoxy resins having bisphenol a skeleton); "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi chemical corporation; "YX6954" manufactured by Mitsubishi chemical corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nissan chemical materials Co., ltd; "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30" manufactured by Mitsubishi chemical corporation; etc.
Specific examples of the polyimide resin include "SLK-6100" manufactured by the more chemical industry Co., ltd., and "RIKACOAT SN20" manufactured by New Japan physical and chemical Co., ltd., and "RIKACOAT PN 20".
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 "Denka butyl 4000-2", "Denka butyl 5000-A", "Denka butyl 6000-C", "Denka butyl 6000-EP" manufactured by electric chemical industry Co; S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, manufactured by the water chemical industry Co., ltd; etc.
Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.
Examples of the polybutadiene resin include a hydrogenated polybutadiene skeleton-containing resin, a hydroxyl-containing polybutadiene resin, a phenolic hydroxyl-containing polybutadiene resin, a carboxyl-containing polybutadiene resin, an acid anhydride-containing polybutadiene resin, an epoxy-containing polybutadiene resin, an isocyanate-containing polybutadiene resin, a urethane-containing polybutadiene resin, and a polyphenylene ether-polybutadiene resin.
Specific examples of the polyamide-imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by eastern spinning corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS9100" and "KS9300" (polyamide-imide containing a polysiloxane skeleton) manufactured by hitachi chemical company.
Specific examples of the polyethersulfone resin include "PES5003P" manufactured by sumitomo chemical company.
Specific examples of the polysulfone resin include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.
Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "ULTEM" manufactured by GE corporation.
Examples of the polycarbonate resin include a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a urethane group-containing carbonate resin. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi gas chemical corporation, "T6002" and "T6001" manufactured by Asahi chemical corporation (Asahi Kasei Chemicals) (polycarbonate diol), and "C-1090" and "C-2090" manufactured by Coleus corporation (polycarbonate diol). Specific examples of the polyether-ether-ketone resin include "SUMIPLOYK" manufactured by Sumitomo chemical Co.
Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polypropylene terephthalate resin, polypropylene naphthalate resin, and polycyclohexane dimethanol terephthalate resin.
(E) The weight average molecular weight (Mw) of the thermoplastic resin is preferably more than 5,000, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 60,000 or less, particularly preferably 50,000 or less.
The content of the thermoplastic resin (E) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 0.2 mass% or more, preferably 5 mass% or less, more preferably 3 mass% or less, and particularly preferably 2 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The content of the thermoplastic resin (E) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more, preferably 10 mass% or less, more preferably 7.5 mass% or less, and particularly preferably 6 mass% or less, based on 100 mass% of the resin component in the resin composition.
[ (F) curing accelerator ]
The resin composition according to one embodiment of the present invention may further contain (F) a curing accelerator as an optional component in addition to the above-described components (a) to (E). The curing accelerator (F) as the component (F) does not contain any substances belonging to the above-mentioned components (A) to (E). (F) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (a) epoxy resin.
Examples of the curing accelerator (F) include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. Among them, imidazole-based curing accelerators are preferable. (F) The curing accelerator may be used alone or in combination of 1 or more than 2.
Examples of the phosphorus-based curing accelerator include: aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydrohexahydrophthalate, tetrabutylphosphonium 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenoxy, and di-t-butyldimethyl phosphonium tetraphenylborate; aromatic phosphonium salts such as methyltriphenyl phosphonium bromide, ethyltriphenyl phosphonium bromide, propyltriphenyl phosphonium bromide, butyltriphenyl phosphonium bromide, benzyltriphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyltrimethyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra-p-tolylborate, triphenylethyl phosphonium tetraphenyl borate, tris (3-methylphenyl) ethyl phosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenyl) ethane, 1, 3-bis (diphenyl) propane, bis (2, 2 '-diphenyl) phosphine, bis (2, 2' -diphenyl) phosphine, etc.
Examples of urea-based curing accelerators include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; aromatic ureas such as 3-phenyl-1, 1-dimethylurea, 3- (4-chlorophenyl) -1, 1-dimethylurea, 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea, 3- (3-chloro-4-methylphenyl) -1, 1-dimethylurea, 3- (2-methylphenyl) -1, 1-dimethylurea, 3- (4-methylphenyl) -1, 1-dimethylurea, 3- (3, 4-dimethylphenyl) -1, 1-dimethylurea, 3- (4-isopropylphenyl) -1, 1-dimethylurea, 3- (4-methoxyphenyl) -1, 1-dimethylurea, 3- (4-nitrophenyl) -1, 1-dimethylurea, 3- [4- (4-methoxyphenoxy) phenyl ] -1, 1-dimethylurea, 3- [4- (4-chlorophenoxy) phenyl ] -1, 1-dimethylurea, N- (1, 4-phenylene) bis (N ', N ' -dimethylurea, N- (4-dimethylphenyl) bis (N, N ' -dimethylurea, etc.
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] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like.
Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-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 isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing the same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins. Examples of the commercially available imidazole-based curing accelerator include "1B2PZ", "2E4MZ", "2MZA-PW", "2MZ-OK", "2MA-OK-PW", "2PHZ-PW", "Cl1Z-CN", "Cl1Z-CNS", "C11Z-A", which are manufactured by the four kingdom chemical industry Co; "P200-H50" manufactured by Mitsubishi chemical corporation, etc.
Examples of the metal curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include: cobalt (II) acetylacetonate, cobalt (III) acetylacetonate and other organic cobalt complexes, copper (II) acetylacetonate and other organic copper complexes, zinc (II) acetylacetonate and other organic zinc complexes, iron (III) acetylacetonate and other organic iron complexes, nickel (II) acetylacetonate and other organic nickel complexes, manganese (II) acetylacetonate and other organic manganese complexes, and the like. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, and 1, 8-diazabicyclo (5, 4, 0) -undecene. As the amine-based curing accelerator, commercially available ones can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine chemical Co., inc.
The content of the (F) curing accelerator in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.02 mass% or more, particularly preferably 0.03 mass% or more, preferably 1 mass% or less, more preferably 0.5 mass% or less, and particularly preferably 0.3 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The content of the curing accelerator (F) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, particularly preferably 0.1 mass% or more, preferably 2 mass% or less, more preferably 1.5 mass% or less, and particularly preferably 1 mass% or less, based on 100 mass% of the resin component in the resin composition.
[ (G) radical polymerizable Compound ]
The resin composition according to one embodiment of the present invention may further contain (G) an optional radical polymerizable compound as an optional component in addition to the above-described components (a) to (F). The radical polymerizable compound (G) as the component (G) does not contain any of the components (a) to (F). (G) The radical polymerizable compound may be used alone or in combination of 1 or more than 2.
(G) The radical polymerizable compound may have an ethylenically unsaturated bond. (G) The radical polymerizable compound may have an unsaturated hydrocarbon group such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a p-vinylphenyl group, an m-vinylphenyl group, an o-vinylphenyl group, or the like; and radical polymerizable groups such as α, β -unsaturated carbonyl groups such as acryl, methacryl, and maleimide groups (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl). (G) The radical polymerizable compound preferably has 2 or more radical polymerizable groups.
Examples of the (G) radical polymerizable compound include (meth) acrylic radical polymerizable compounds, styrene radical polymerizable compounds, allyl radical polymerizable compounds, maleimide radical polymerizable compounds, and the like.
The (meth) acrylic acid-based radical polymerizable compound is, for example, a compound having 1 or more, preferably 2 or more, acryl groups and/or methacryl groups. Examples of the (meth) acrylic radical polymerizable compound include: low molecular weight (molecular weight less than 1000) aliphatic (meth) acrylate compounds such as cyclohexane-1, 4-dimethanol di (meth) acrylate, cyclohexane-1, 3-dimethanol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1, 8-octanediol di (meth) acrylate, 1, 9-nonanedioldi (meth) acrylate, 1, 10-decanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like; ether-containing (meth) acrylate compounds having a low molecular weight (molecular weight of less than 1000) such as dioxane glycol di (meth) acrylate, 3, 6-dioxa-1, 8-octanediol di (meth) acrylate, 3,6, 9-trioxaundecane-1, 11-diol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 9-bis [4- (2-acryloyloxyethoxy) phenyl ] fluorene, ethoxylated bisphenol a di (meth) acrylate, propoxylated bisphenol a di (meth) acrylate; isocyanurate-containing (meth) acrylate compounds having a low molecular weight (molecular weight of less than 1000), such as tris (3-hydroxypropyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and ethoxylated isocyanurate tri (meth) acrylate; and high molecular weight (molecular weight of 1000 or more) acrylate compounds such as (meth) acrylic acid-modified polyphenylene ether resins. Examples of commercial products of the (meth) acrylic radical polymerizable compound include: "A-DOG" (dioxane glycol diacrylate) manufactured by Xinzhou chemical industry Co., ltd.), "DCP-A" (tricyclodecane dimethanol diacrylate) manufactured by Zosterol chemical Co., ltd., "DCP" (tricyclodecane dimethanol dimethacrylate), "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) manufactured by Japanese chemical Co., ltd., "KAYARAD R-604" (dioxane glycol diacrylate), and "SA9000" or "SA9000-111" (methacrylic acid modified polyphenylene ether) manufactured by Saint Innovative plastics (SABIC Innovative Plastics) Co.
The styrene-based radical polymerizable compound is, for example, a compound having 1 or more, preferably 2 or more vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene-based radical polymerizable compound include: styrene compounds having a low molecular weight (molecular weight of less than 1000) such as divinylbenzene, 2, 4-divinylbenzene, 2, 6-divinylnaphthalene, 1, 4-divinylnaphthalene, 4' -divinylbiphenyl, 1, 2-bis (4-vinylphenyl) ethane, 2-bis (4-vinylphenyl) propane, and bis (4-vinylphenyl) ether; and high molecular weight (molecular weight of 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resins and styrene-divinylbenzene copolymers. Examples of commercial products of the styrene-based radical polymerizable compound include: "ODV-XET (X03)", "ODV-XET (X04)", "ODV-XET (X05)" (styrene-divinylbenzene copolymer), and "OPE-2St 1200", "OPE-2St 2200" (vinylbenzyl modified polyphenylene ether resin) by Mitsubishi gas chemical company.
The allyl radical polymerizable compound is, for example, a compound having 1 or more, preferably 2 or more allyl groups. Examples of the allyl radical polymerizable compound include: aromatic carboxylic acid allyl ester compounds such as diallyl phthalate (Diallyl Diphenate), triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2, 6-naphthalate, diallyl 2, 3-naphthalate, and the like; allyl isocyanurate compounds such as 1,3, 5-triallyl isocyanurate and 1, 3-diallyl-5-glycidyl isocyanurate; epoxy group-containing aromatic allyl compounds such as 2, 2-bis [ 3-allyl-4- (glycidoxy) phenyl ] propane; benzoxazine-containing aromatic allyl compounds such as bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane; ether-containing aromatic allyl compounds such as 1,3, 5-triallylether benzene; allylsilane compounds such as diallyldiphenylsilane, and the like. Examples of the commercial products of the allyl radical polymerizable compound include "TAIC" (1, 3, 5-triallyl isocyanurate) manufactured by Japanese chemical Co., ltd., "DAD" (diallyl phthalate) manufactured by Nisshoku Techno Fine Chemical, and "TRIAM-705" (triallyl trimellitate) manufactured by Wako pure chemical industries, trade names "DAND" (diallyl 2, 3-naphthoate) manufactured by Japanese distillation industries, and "ALP-d" (bis [ 3-allyl-4- (3, 4-dihydro-2H-1, 3-benzoxazin-3-yl) phenyl ] methane) manufactured by Japanese chemical Co., and "RE-810NM" (2, 2-bis [ 3-allyl-4- (glycidoxy) phenyl ] propane) manufactured by Japanese chemical Co., ltd., and "DA-MGIC" (1, 3-diallyl-5-glycidylisocyanurate) manufactured by Japanese chemical Co., ltd.
The maleimide-based radically polymerizable compound is, for example, a compound having 1 or more maleimide groups, preferably 2 or more maleimide groups. The maleimide-based radically polymerizable compound may be an aliphatic maleimide compound having an aliphatic amine skeleton or an aromatic maleimide compound having an aromatic amine skeleton. Examples of commercial products of maleimide-based radical polymerizable compounds include: "SLK-2600" by Xinyue chemical industry Co., ltd., "BMI-1500" by design molecule (Designer Molecules) Co., ltd., "BMI-1700", "BMI-3000J", "BMI-689", "BMI-2500" (maleimide compound containing dimer diamine structure), "BMI-6100" by design molecule Co., ltd., "aromatic maleimide compound", MIR-5000-60T "by Japanese chemical company, MIR-3000-70MT" (biphenyl aralkyl maleimide compound), "BMI-70" by KI chemical industry Co., ltd., BMI-2300"," BMI-TMH "by large and chemical industry Co., etc. Further, as the maleimide-based radical polymerizable compound, a maleimide resin (a maleimide compound having an indane ring skeleton) disclosed in Japanese patent application laid-open No. 2020-500211 can be used.
(G) The ethylenically unsaturated bond equivalent of the radical polymerizable compound is preferably 20g/eq to 3,000g/eq, more preferably 50g/eq to 2,500g/eq, still more preferably 70g/eq to 2,000g/eq, and particularly preferably 90g/eq to 1,500g/eq. The ethylenically unsaturated bond equivalent means the mass of the radical polymerizable compound per 1 equivalent of ethylenically unsaturated bond.
(G) The weight average molecular weight (Mw) of the radical polymerizable compound is preferably 40,000 or less, more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, and may be, for example, 150 or more.
The content of the radical polymerizable compound (G) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 1 mass% or more, preferably 15 mass% or less, more preferably 10 mass% or less, and particularly preferably 5 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
The content of the radical polymerizable compound (G) in the resin composition may be 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, particularly preferably 1 mass% or more, preferably 15 mass% or less, more preferably 10 mass% or less, and particularly preferably 7.5 mass% or less, based on 100 mass% of the resin component in the resin composition.
[ (H) optional additives ]
The resin composition according to one embodiment of the present invention may contain (H) an optional additive as an optional nonvolatile component in addition to the above-described components (a) to (G). Examples of the optional additive (H) include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; thermosetting resins other than epoxy resins, such as epoxy acrylate resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenolic resins, melamine resins, and silicone resins; organic fillers such as rubber particles; organocopper compounds, organozinc compounds, organocobalt compounds, and the like; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as Benton and montmorillonite; an antifoaming agent such as an organosilicon antifoaming agent, an acrylic antifoaming agent, a fluorine antifoaming agent, and a vinyl resin antifoaming agent; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improving agent such as ureidosilane; an adhesion-imparting agent such as a triazole-based adhesion-imparting agent, a tetrazole-based adhesion-imparting agent, and a triazine-based adhesion-imparting agent; antioxidants such as hindered phenol antioxidants; fluorescent whitening agents such as stilbene derivatives; a surfactant such as a fluorine-based surfactant and a silicone-based surfactant; flame retardants such as phosphorus flame retardants (for example, phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (for example, melamine sulfate), halogen flame retardants, and inorganic flame retardants (for example, antimony trioxide); a phosphate-based dispersant, a polyoxyalkylene-based dispersant, an alkyne (acetylene) -based dispersant, a silicone-based dispersant, an anionic dispersant, a cationic dispersant, and the like; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic anhydride stabilizers. (H) The optional additives may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
[ (I) solvent ]
The resin composition according to the present embodiment may contain a solvent (I) as an optional volatile component in addition to the nonvolatile components such as the above-described components (a) to (H). As the solvent (I), an organic solvent is generally used. Examples of the organic solvent include: ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole, and the like; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol ethyl ether acetate (ethyl diglycol acetate), γ -butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane and methylcyclohexane; aromatic solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (I) The solvent may be used alone or in combination of 1 or more than 2.
(I) The content of the solvent is not particularly limited, and may be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, or 0 mass% or less, based on 100 mass% of the total components in the resin composition.
[ method for producing resin composition ]
The resin composition according to one embodiment of the present invention can be produced, for example, by mixing the above-described components. The above components may be partially or completely mixed at the same time or may be mixed sequentially. The temperature can be set appropriately during the mixing of the components, and therefore heating and/or cooling can be performed temporarily or throughout. In addition, stirring or shaking may be performed during the mixing of the components.
[ physical Properties of resin composition ]
The above resin composition can be cured by heat. Therefore, the resin composition can be thermally cured to obtain a cured product of the resin composition. In general, among the components contained in the resin composition, the volatile components such as the (I) solvent may volatilize by the heat at the time of heat curing, but the nonvolatile components such as the components (a) to (H) may not volatilize by the heat at the time of heat curing. Accordingly, the cured product of the resin composition may contain a nonvolatile component of the resin composition or a reaction product thereof.
The resin composition according to one embodiment of the present invention can generally give a cured product having a low dielectric loss tangent. For example, when the dielectric loss tangent of a cured product is measured under the conditions described in the item [ dielectric properties ] of examples described later, a low dielectric loss tangent can be obtained. The dielectric loss tangent of the cured product is preferably 0.0040 or less, more preferably 0.0035 or less, and particularly preferably 0.0030 or less. The lower limit is not particularly limited, and may be, for example, 0.0001 or more.
The resin composition according to one embodiment of the present invention can generally provide a cured product having excellent crack resistance. For example, when the crack resistance of the cured product is determined under the conditions described in the "crack resistance" item of the example described below, a high yield can be obtained. The yield of the cured product is preferably 50% or more, more preferably 75% or more, particularly preferably 90% or more, and usually 100% or less.
The resin composition according to one embodiment of the present invention can generally provide a cured product excellent in adhesion to a plated conductor layer. That is, when a conductor layer is formed on a cured product of a resin composition by plating, the conductor layer and the cured product can have high adhesion. For example, when the plating peel strength is measured under the conditions described in the following item [ adhesion to a plated conductor layer ] of examples, the plating peel strength can be increased. The plating peel strength indicates the amount of force required to peel the conductor layer formed on the cured product of the resin composition by plating, and the greater the plating peel strength, the more excellent the adhesion to the plated conductor layer. The plating peel strength is preferably 0.30kgf/cm or more, more preferably 0.35kgf/cm or more, and particularly preferably 0.40kgf/cm or more.
[ use of resin composition ]
The resin composition according to one embodiment of the present invention can be used as a resin composition for insulation, and in particular, can be suitably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer). For example, the resin composition according to one embodiment of the present invention can be used as a resin composition for forming an insulating layer of a printed wiring board, and can be suitably used as a resin composition for forming an interlayer insulating layer (a resin composition for interlayer insulation).
The resin composition according to one embodiment of the present invention can be used as a resin composition for forming a rewiring forming layer (a resin composition for forming a rewiring forming layer). The rewiring-forming layer means an insulating layer for forming a rewiring layer. The rewiring layer is a conductor layer formed on the rewiring layer serving as an insulating layer. For example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition according to the present embodiment can be used as a resin composition for forming a rewiring forming layer. In addition, when the semiconductor chip package is manufactured by the following steps (1) to (6), a rewiring layer may be further formed on the sealing layer;
(1) A step of laminating a temporary fixing film on the base material,
(2) A step of temporarily fixing the semiconductor chip on the temporary fixing film,
(3) A step of forming a sealing layer on the semiconductor chip,
(4) A step of peeling the base material and the temporary fixing film from the semiconductor chip,
(5) A step of forming a rewiring forming layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film are peeled, and
(6) And forming a rewiring layer as a conductor layer on the rewiring layer.
The resin composition according to one embodiment of the present invention is widely used in applications using a resin composition, such as a sheet-like laminate material such as a resin sheet or a prepreg, a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, and a component embedding resin.
[ sheet laminate ]
The resin composition according to one embodiment of the present invention can be used by coating in the form of a varnish, but is industrially preferably used in the form of a sheet laminate containing the resin composition.
As the sheet-like laminate, a resin sheet and a prepreg shown below are preferable.
In one embodiment of the present invention, a resin sheet includes a support and a resin composition layer provided on the support. The resin composition layer is formed of the resin composition according to the present embodiment. Therefore, the resin composition layer generally contains a resin composition, preferably contains only a resin composition.
The thickness of the resin composition layer is preferably 50 μm or less, more preferably 40 μm or less, from the viewpoints of thinning of the printed wiring board and providing a cured product excellent in insulation even if the cured product of the resin composition is a film. The lower limit of the thickness of the resin composition layer is not particularly limited, and may be 5 μm or more, 10 μm or more, or the like.
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 formed of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN"), polycarbonates (hereinafter, abbreviated as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The surface of the support to be bonded to the resin composition layer may be subjected to a matting treatment, a corona treatment, or an antistatic treatment.
As the support, a support with a release layer having a release layer on a surface to be bonded to the resin composition layer can be used. The release agent used in the release layer of the support having a release layer includes, for example, 1 or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. As the support having a release layer, commercially available ones can be used, and examples thereof include "SK-1", "AL-5", "AL-7", lumiror T60", by Toli, purex", by Di, and "Unipel" by UNITKA, you Niji, which are PET films having a release layer containing an alkyd-based release agent as a main component.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. In the case of using the support with a release layer, the thickness of the entire support with a release layer is preferably in the above range.
In one embodiment, the resin sheet may further include an optional layer as needed. Examples of the optional layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and selected for the support. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, dust adhesion to the surface of the resin composition layer or damage to the surface of the resin composition layer can be suppressed.
The resin sheet can be produced, for example, by: a resin composition layer is formed by directly applying a liquid (varnish-like) resin composition to a support using a die coater or the like, or by dissolving a resin composition in a solvent to prepare a liquid (varnish-like) resin composition, applying the liquid (varnish-like) resin composition to a support using a die coater or the like, and drying the same.
Examples of the organic solvent include the same solvents as those described as components of the resin composition. The organic solvent may be used alone or in combination of 1 or more than 2.
Drying can be performed by a known method such as heating and blowing hot air. The drying conditions are not particularly limited so that the content of the organic solvent in the resin composition layer becomes generally 10 mass% or less, preferably 5 mass% or less. The drying conditions vary depending on the boiling point of the organic solvent in the resin varnish, and for example, when a resin varnish containing 30 to 60 mass% of the organic solvent is used, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.
The resin sheet may be wound into a roll for storage. When the resin sheet has a protective film, the protective film can be peeled off for use.
In one embodiment, the prepreg may be produced by a method including impregnating a sheet-like fibrous base material with the resin composition according to the present embodiment.
As the sheet-like fibrous substrate used in the prepreg, for example, a substrate commonly used as a substrate for the prepreg, such as a glass cloth, an aramid nonwoven fabric, a liquid crystal polymer nonwoven fabric, or the like, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, further preferably 30 μm or less, and particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited, and is usually 10 μm or more.
The prepreg can be produced by a hot melt method, a solvent method, or the like.
The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet.
The sheet-like laminate is suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board).
[ printed wiring Board ]
The printed wiring board according to one embodiment of the present invention includes an insulating layer including a cured product obtained by curing the resin composition according to the present embodiment. The printed wiring board can be manufactured, for example, by a method including the steps of (I) and (II) below:
(I) Forming a resin composition layer on the inner substrate;
(II) a step of curing the resin composition layer to form an insulating layer.
The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. In addition, the substrate may have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both surfaces of the substrate is sometimes referred to as an "inner layer circuit substrate". In addition, intermediate products to be further formed into an insulating layer and/or a conductor layer at the time of manufacturing a printed wiring board are also included in the aforementioned "inner layer substrate". When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.
The formation of the resin composition layer on the inner layer substrate is preferably performed using the resin sheet described above. For example, the resin composition layer may be formed by a method including: the resin sheet is laminated on the inner layer substrate in such a manner that the resin composition layer of the resin sheet is bonded to the inner layer substrate. Lamination of the inner substrate and the resin sheet can be performed by, for example, thermally pressing the resin sheet against the inner substrate from the support side. As a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the heat pressure bonding member is not directly pressed against 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 lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably 60 to 160 ℃, more preferably 80 to 140 ℃, the thermocompression bonding pressure is preferably 0.098 to 1.77MPa, more preferably 0.29 to 1.47MPa, and the thermocompression bonding time is preferably 20 to 400 seconds, more preferably 30 to 300 seconds. The lamination is preferably performed under reduced pressure of 26.7hPa or less.
Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by the company name machine, vacuum applicators (vacuum applicator) manufactured by Nikko-Materials, and batch vacuum pressurized laminators.
After lamination, the heat and pressure bonding member is pressed from the support body side at normal pressure (atmospheric pressure), for example, whereby the laminated resin sheets can be smoothed. The pressing conditions for the smoothing treatment may be set to the same conditions as those for the above-described lamination of the heat press-bonding. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.
The support may be removed between the step (I) and the step (II), or may be removed after the step (II).
In the step (II), the resin composition layer is cured to form an insulating layer formed of a cured product of the resin composition. The curing of the resin composition layer is generally performed by thermal curing. As specific curing conditions of the resin composition layer, conditions generally employed in forming an insulating layer of a printed wiring board can be used.
For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition and the like, and in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, and even more preferably 170 to 210 ℃. The curing time may be preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and still more preferably 15 minutes to 100 minutes.
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes at a temperature of 50 ℃ to 150 ℃, preferably 60 ℃ to 140 ℃, more preferably 70 ℃ to 130 ℃ before the resin composition layer is thermally cured.
In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. The steps (III) to (V) may be performed according to various methods known to those skilled in the art, which can be used for manufacturing a printed wiring board. When the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). The insulating layer and the conductor layer may be formed repeatedly in the steps (I) to (V) as needed, to form a multilayer wiring board.
In other embodiments, the printed wiring board may be manufactured using the prepreg described above. The production method is basically the same as in the case of using a resin sheet.
The step (III) is a step of forming a hole in the insulating layer, and thus holes such as a via hole and a through hole can be formed in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The size and shape of the holes may be appropriately determined according to the design of the printed wiring board.
The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the contamination is also performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions used in forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid.
Examples of the swelling liquid used in the roughening treatment include an alkali solution and a surfactant solution, and alkali solutions are preferable. The alkali solution is more preferably a sodium hydroxide solution or a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by America Japan (ATOTECH JAPAN), inc. The swelling treatment with the swelling solution can be performed, for example, by immersing the insulating layer in the swelling solution at 30 to 90 ℃ for 1 to 20 minutes. From the viewpoint of suppressing swelling of the resin of the insulating layer to a proper level, it is preferable to impregnate the insulating layer in a swelling liquid at 40 to 80 ℃ for 5 to 15 minutes.
Examples of the oxidizing agent used in the roughening treatment include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 100 ℃ for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10 mass%. Examples of the commercially available oxidizing agent include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Anmeite Japan Co., ltd.
The neutralization solution used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by ambett japan corporation. The neutralization solution-based treatment may be performed by immersing the treated surface, on which the roughening treatment by the oxidizing agent is completed, in the neutralization solution at 30 to 80 ℃ for 5 to 30 minutes. In view of handling properties, it is preferable to dip the object subjected to the roughening treatment by the oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.
In one embodiment, the surface of the insulating layer after roughening treatment has an arithmetic average roughness (Ra) of preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The root mean square roughness (Rq) of the roughened insulating layer surface is preferably 500nm or less, more preferably 400nm or less, and still more preferably 300nm or less. The lower limit is not particularly limited, and may be, for example, 1nm or more, 2nm or more, or the like. The arithmetic average roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact surface roughness meter.
The step (V) is a step of forming a conductor layer, and the conductor layer is formed on the insulating layer. The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and examples of the alloy layer include a layer formed of an alloy of two or more metals selected from the group described above (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility of conductor layer formation, cost, ease of patterning, and the like, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy is preferable, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of nickel-chromium alloy is more preferable, and a single metal layer of copper is further preferable.
The conductor layer may have a single-layer structure, or may have a multilayer structure in which two or more single metal layers or alloy layers each made of a different metal or alloy are stacked. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.
The thickness of the conductor layer is usually 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the design of the desired printed wiring board.
In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of an insulating layer using a conventionally known technique such as a half-addition method or a full-addition method, and it is preferable to form the conductor layer by a half-addition method from the viewpoint of ease of manufacturing. Hereinafter, an example of forming a conductor layer by a half-additive method is shown.
First, a plating seed layer is formed on the surface of an insulating layer by electroless plating. Next, a mask pattern exposing a part of the plating seed layer is formed on the formed plating seed layer corresponding to the desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like, whereby a conductor layer having a desired wiring pattern can be formed.
In other embodiments, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using a metal foil on the insulating layer.
The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil manufactured by JX Nitshi metal Co., ltd., JXUT-III foil, 3EC-III foil manufactured by Mitsui metal mine Co., ltd., TP-III foil, and the like.
[ semiconductor device ]
A semiconductor device according to an embodiment of the present invention includes the printed wiring board. Semiconductor devices may be fabricated using printed wiring boards.
Examples of the semiconductor device include various semiconductor devices that can be used for electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, aircraft, and the like).
Examples
The present invention will be specifically described below with reference to examples. However, the present invention is not limited by these examples. Hereinafter, "part" and "%" representing amounts refer to "part by mass" and "% by mass", respectively, unless otherwise specifically stated. The temperature conditions and pressure conditions when the temperature is not particularly specified are room temperature (25 ℃) and atmospheric pressure (1 atm).
Example 1
While stirring, 5 parts of a liquid epoxy resin (ZX 1059, manufactured by Nikka chemical materials Co., ltd., 1:1 mixture (mass ratio) of bisphenol A type epoxy resin and bisphenol F type epoxy resin), and 15 parts of a biphenyl type epoxy resin (NC 3000H, manufactured by Japanese chemical materials Co., ltd., epoxy equivalent of about 290 g/eq.) were dissolved in a mixed solvent of 20 parts of toluene and 20 parts of MEK by heating. After cooling the obtained solution to room temperature, 42 parts of an active ester curing agent (HP-B-8151-62T, manufactured by DIC Co., ltd., active group equivalent of 238g/eq., toluene solution having 62% of solid content) and 42 parts of a triazine skeleton-containing phenol curing agent (LA-3018-50P, manufactured by DIC Co., ltd., hydroxyl equivalent of about 151g/eq., 2-methoxypropanol solution having 50% of solid content) were mixed, 4 parts of a phenoxy resin (YX 7553BH30, manufactured by Mitsubishi chemical Co., ltd., 1:1 solution of MEK and cyclohexanone having 30% by mass of nonvolatile components), 10 parts of a silicone-containing resin (resin in which trimethoxysilyl groups were introduced into side chains of a direct addition unit of a styrene-butadiene copolymer, manufactured by Xinyue chemical industry Co., ltd. "X-12-1281C", number) Average molecular weight of 5,000), 1.5 parts of a curing accelerator (MEK solution having a solid content of 10% by mass, manufactured by the chemical industry Co., ltd. "1B2 PZ"), 4 parts of an inorganic filler (spherical silica surface-treated with an amine-based silane coupling agent (manufactured by the chemical industry Co., ltd. "KBM 573") (manufactured by the chemical industry Co., ltd. "SO-C2", manufactured by the Utility Co., ltd. "having an average particle diameter of 0.5 μm, and a specific surface area of 5.8 m) 2 150 parts of (g)) was uniformly dispersed by a high-speed rotary mixer to obtain a resin composition 1.
Example 2
Resin composition 2 was obtained in the same manner as in example 1 except that 6 parts of a carbodiimide-based curing agent (approximately 216g/eq of active group equivalent, 50% solids toluene solution, "V-03", manufactured by Niqing textile chemical Co., ltd.) was added.
Example 3
Resin composition 3 was obtained in the same manner as in example 1 except that 6 parts of a thermosetting resin having a phenylene ether structure (a (meth) acrylic radical polymerizable compound "SA9000" manufactured by Saint Innovative plastics Co., ltd., 50% solids toluene solution) was added.
Example 4
Resin composition 4 was obtained in the same manner as in example 1, except that 3 parts of a maleimide compound (BMI-689, manufactured by Kyowa Co., ltd., maleimide group equivalent was used) was added.
Example 5
Resin composition 5 was obtained in the same manner as in example 2 except that 42 parts of an active ester curing agent (toluene solution having an active group equivalent of 238g/eq. And a solid content of 62%) was used instead of 42 parts of the active ester curing agent (methyl amyl ketone solution having an active group equivalent of 199g/eq. And a solid content of 65% by mass, manufactured by Air Water company, "PC1300-02-65 MA").
Example 6
Resin composition 6 was obtained in the same manner as in example 2 except that the amount of the silicon-containing resin (X-12-1281C, made by Xinyue chemical industries Co., ltd.) was changed from 1.5 parts to 4.5 parts.
Example 7
Resin composition 7 was obtained in the same manner as in example 2 except that 1.5 parts of the silicon-containing resin (X-12-1281C, made by Xinyue chemical industry Co., ltd.) was replaced with 1.5 parts of another silicon-containing resin (a resin in which trimethoxysilyl groups were introduced into side chains of direct addition units of a styrene-butadiene copolymer, and the number average molecular weight was 9,000, made by Xinyue chemical industry Co., ltd.).
Example 8
1.5 parts of a silicon-containing resin (X-12-1281C, made by Xinyue chemical industry Co., ltd.) was replaced with another silicon-containing resin (a resin in which triethoxysilyl groups were introduced into side chains of direct addition units of a styrene-butadiene copolymer, "X-12-1281A-ES, made by Xinyue chemical industry Co., ltd.) and having a number average molecular weight of 9,500, may correspond to a resin comprising a structure represented by formula (2), and in the structure, j=52, k=0, l=22, m=29, n=3, Y is ethylene, R 46 Is ethyl. ) 1.5 parts by weight of a resin composition 8 was obtained in the same manner as in example 5.
Comparative example 1
A comparative resin composition 1 was obtained in the same manner as in example 1 except that 1.5 parts of a silicon-containing resin (X-12-1281C, made by Xinyue chemical industry Co., ltd.) was not used.
Comparative example 2
Resin composition 2 for comparison was prepared in the same manner as in example 1 except that 1.5 parts of a silicon-containing resin (X-12-1281C, made by Xinyue chemical Co., ltd.) was used, 1.4 parts of a styrene-diene copolymer (Ricon 184, made by Ke Lei Weili Co., ltd.) and 0.1 part of an alkoxysilane compound (epoxysilane KBM403, made by Xinyue chemical Co., ltd.) were used, and the miscibility was poor, whereby a uniform resin composition was not obtained.
[ production of resin sheet ]
As a support, a polyethylene terephthalate film (LumirrorR 80, manufactured by Toli Co., ltd., thickness: 38 μm, softening point: 130 ℃ C.) having been subjected to a mold release treatment with an alkyd resin-based mold release agent (manufactured by Lendesco Co., ltd. "AL-5") was prepared.
Resin compositions 1 to 8 and comparative resin composition 1 were uniformly applied to a support by a die coater so that the thickness of the dried resin composition layer became 30. Mu.m, and dried at 70℃to 95℃for 3 minutes, whereby a resin composition layer was formed on the support. Next, a rough surface of a polypropylene film (ALPHAN MA-411, manufactured by Oji F-Tex Co., ltd., thickness of 15 μm) was bonded to the surface of the resin composition layer which was not bonded to the support, as a protective film. Thus, a resin sheet a having a support, a resin composition layer, and a protective film in this order was obtained.
[ adhesion to the plated conductor layer ]
(1) Preparation of inner substrate
A glass cloth base epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by Songshi Co., ltd.) having an inner layer circuit formed on both sides thereof was prepared as an inner layer substrate. The inner substrate was roughened by etching both surfaces thereof with a microetching agent (CZ 8101, manufactured by MEC Co.) to 1 μm.
(2) Lamination of resin sheets
The protective film was peeled off from the resin sheet a to expose the resin composition layer. A batch vacuum press laminator (CVP 700, manufactured by Nikko-Materials Co., ltd., 2-stage lamination laminator) was used to laminate the resin composition layer on both sides of the inner layer substrate so as to contact the inner layer substrate. Lamination is carried out by: the pressure was reduced for 30 seconds to adjust the air pressure to 13hPa or less, and then the pressure was applied at 120℃under a pressure of 0.74MPa for 30 seconds. Next, hot pressing was performed at 100℃under a pressure of 0.5MPa for 60 seconds.
(3) Thermosetting of resin composition layer
Then, the inner substrate laminated with the resin sheet was put into an oven at 130 ℃ for 30 minutes to heat, then transferred into an oven at 180 ℃ for 30 minutes to heat the resin composition layer, and an insulating layer formed of a cured product of the resin composition was formed. Then, the support was peeled off to obtain a cured substrate a having an insulating layer, an inner substrate, and an insulating layer in this order.
(4) Roughening treatment
For the insulating layer of the cured substrate a, a desmear treatment as a roughening treatment is performed. As the desmear treatment, the following wet desmear treatment was performed.
(Wet contamination removal treatment)
The cured substrate a was immersed in a swelling solution (aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide, manufactured by ameter japan corporation "Swelling Dip Securiganth P") at 60 ℃ for 5 minutes, then immersed in an oxidizing agent solution (aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ℃ for 20 minutes, then immersed in a neutralization solution (aqueous solution of sulfuric acid, manufactured by ameter japan corporation "Reduction Solution Securiganth P") at 40 ℃ for 5 minutes, and then dried at 80 ℃ for 15 minutes.
(5) Formation of conductor layer
A conductor layer is formed on the roughened surface of the insulating layer by a semi-additive method. That is, the roughened cured substrate A was subjected to a roughening treatment at 40℃to contain PdCl 2 After immersing in the electroless plating solution for 5 minutes, immersing in the electroless copper plating solution at 25℃for 20 minutes. Then, the resist layer was formed by annealing after heating at 150 ℃ for 30 minutes, and patterning was performed by etching. Then, copper sulfate was electrolytically plated to form a 30 μm thick conductor layer, and annealing was performed at 200℃for 60 minutes. The obtained substrate was referred to as "evaluation substrate B".
(6) Evaluation of adhesion to plated conductor layer
The peel strength of the insulating layer and the plated conductor layer was measured in accordance with japanese industrial standards (JIS C6481). Specifically, a scribe line surrounding a rectangular portion having a width of 10mm and a length of 100mm was formed on the conductor layer of the evaluation substrate B. One end of the rectangular portion was peeled off and held by a jig, and the load (kgf/cm) at room temperature when peeled off at a speed of 50 mm/min in the vertical direction was measured to determine the peel strength (plating peel strength). A tensile tester (TSE Co., ltd. "AC-50C-SL") was used for the measurement.
[ dielectric Property ]
The protective film was peeled off from the resin sheet a produced in examples and comparative examples, and the resin composition layer was thermally cured by heating at 200 ℃ for 90 minutes. Then, the support is peeled off to obtain a cured product of the resin composition. The obtained cured product was referred to as "cured product for evaluation C". The cured product C for evaluation was cut to obtain test pieces having a width of 2mm and a length of 80 mm. For this test piece, dielectric loss tangent was measured by using "HP8362B" manufactured by Agilent technologies, inc., using a cavity perturbation method under conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The measurement was performed on 3 test pieces, and an average value was calculated.
[ crack resistance ]
(1) Lamination of resin sheets
An inner layer substrate (MCL-E700G manufactured by hitachi chemical company) having a circuit conductor (copper) formed by a wiring pattern having a line width/line spacing (L/S) =8 μm/8 μm on both sides thereof was prepared (the thickness of the conductor layer was 35 μm, the total thickness was 0.4mm, and the residual copper ratio was 40%). The resin sheet a from which the protective film is peeled is laminated on both surfaces of the inner layer substrate so that the resin composition layer is in contact with the inner layer substrate. The lamination is performed by: a vacuum laminator (MVLP-500 manufactured by Kyowa Kagaku Co., ltd.) was used, vacuum suction was performed at 120℃for 30 seconds, and then pressing was performed from the support via a heat-resistant rubber at 120℃under a pressure of 0.7MPa for 30 seconds. Next, pressing was performed at 120 ℃ and a pressure of 0.55MPa for 60 seconds using SUS end plates under atmospheric pressure.
(2) Thermosetting of resin composition layer
Then, the inner substrate laminated with the resin sheet was put into an oven at 130 ℃ for 30 minutes to heat, then transferred into an oven at 180 ℃ for 30 minutes to heat, and the resin composition layer was thermally cured to form an insulating layer formed of a cured product of the resin composition. Then, the support was peeled off to obtain a cured substrate D having an insulating layer, an inner substrate, and an insulating layer in this order.
(3) Roughening treatment
For the cured substrate D, a desmear treatment as a roughening treatment is performed. The desmear treatment was carried out in the same manner as described in the above section [ adhesion to a plated conductor layer ] (wet desmear treatment).
(4) Evaluation of crack resistance
The surface of the insulating layer located directly above the wiring pattern (L/s=8 μm/8 μm) of the inner layer substrate was observed from among the surface of the insulating layer after the desmear treatment. For 100 samples, it was confirmed whether or not cracks were generated on the surface of the insulating layer along the pattern shape of the inner layer substrate, and the proportion of samples in which no cracks were generated was determined. The ratio was calculated as "yield", and the yield was evaluated as "o" and the yield was evaluated as "x" for 50% or more.
Results (results)
The results of the above examples and comparative examples are shown in tables 1 and 2 below. In comparative example 2, the peel strength, dielectric loss tangent and crack resistance were not evaluated.
TABLE 1
TABLE 1 results for examples 1-5
TABLE 2
TABLE 2 results for examples 6-8 and comparative examples 1-2
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Claims (18)

1. A resin composition comprising:
(A) An epoxy resin,
(B) Curing agent
(C) An alkoxysilyl group-containing and hydrogenated conjugated diene-aromatic vinyl copolymer resin.
2. The resin composition according to claim 1, wherein,
(C) The components comprise: (c1) Conjugated diene compound units which can be hydrogenated, and (c 2) aromatic vinyl compound units,
an alkoxysilyl group is bonded to a part or all of the conjugated diene compound units which may be hydrogenated in (c 1).
3. The resin composition according to claim 2, wherein,
(c1) The conjugated diene compound unit which can be hydrogenated is a butadiene unit which can be hydrogenated,
(c2) The aromatic vinyl compound unit is a styrene unit.
4. The resin composition according to claim 2, wherein,
(c1) Conjugated diene compound units which can be hydrogenated contain a direct addition unit,
an alkoxysilyl group is bonded to a part or the whole of the side chain of the direct addition unit.
5. The resin composition according to claim 2, wherein the amount of the aromatic vinyl compound unit (C2) is 15 to 50 mass% based on 100 mass% of the component (C).
6. The resin composition according to claim 1, wherein component (C) contains (C3) alkenylalkoxysilane units.
7. The resin composition according to claim 1, wherein the component (C) comprises a structure represented by the following formula (1),
In the formula (1), the components are as follows,
R 1 ～R 31 、R 34 ～R 40 r is R 43 ～R 45 Each independently ofIn the vertical place a hydrogen atom or a monovalent hydrocarbon group,
x represents a single bond or a divalent linking group,
R 32 、R 33 、R 41 r is R 42 Each independently represents a monovalent hydrocarbon group,
ar represents an aryl group optionally having a substituent,
a. b, c and d each independently represent an integer of 0 or more,
e and f represent integers of 0 or more satisfying e+f 1 or more,
g represents an integer of 1 or more,
h and i each independently represent an integer of 1 to 3,
the order of the repeating units a, b, c, d, e, f, and g is arbitrary.
8. The resin composition according to claim 1, wherein the component (C) comprises a structure represented by the following formula (2),
in the formula (2), the amino acid sequence of the compound,
y represents a single bond or a divalent hydrocarbon group,
R 46 r is R 47 Each independently represents a monovalent hydrocarbon group,
j and k each independently represent an integer of 0 or more,
l and m each independently represent an integer greater than 0,
n represents an integer of 1 to 3,
the order of the repeating units j, k, l and m is arbitrary.
9. The resin composition according to claim 1, wherein the amount of the component (C) is 0.01 to 10% by mass based on 100% by mass of the nonvolatile component of the resin composition.
10. The resin composition according to claim 1, wherein (B) the curing agent comprises an active ester-based curing agent.
11. The resin composition according to claim 1, wherein (D) an inorganic filler is contained.
12. The resin composition according to claim 11, wherein the amount of the (D) inorganic filler is 50% by mass or more and 90% by mass or less relative to 100% by mass of the nonvolatile component of the resin composition.
13. The resin composition according to claim 1, which is used for forming an insulating layer.
14. A cured product of the resin composition according to any one of claims 1 to 13.
15. A sheet-like laminate comprising the resin composition according to any one of claims 1 to 13.
16. A resin sheet, comprising:
support body
A resin composition layer formed of the resin composition according to any one of claims 1 to 13, provided on the support.
17. A printed wiring board is provided with: an insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 13.
18. A semiconductor device comprising the printed wiring board according to claim 17.
CN202310142718.3A 2022-02-25 2023-02-21 Resin composition Pending CN116656085A (en)

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