CN116396444A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN116396444A
CN116396444A CN202211710590.8A CN202211710590A CN116396444A CN 116396444 A CN116396444 A CN 116396444A CN 202211710590 A CN202211710590 A CN 202211710590A CN 116396444 A CN116396444 A CN 116396444A
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Prior art keywords
resin composition
group
mass
resin
epoxy resin
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Inventor
藤岛祥平
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4611—Manufacturing multilayer circuits by laminating two or more circuit boards
    • H05K3/4626—Manufacturing multilayer circuits by laminating two or more circuit boards characterised by the insulating layers or materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium

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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)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Epoxy Resins (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a resin composition which can obtain a cured product with excellent crack resistance. The solution of the present invention is a resin composition comprising (A) an epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a curing accelerator, wherein component (C) comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.

Description

Resin composition
Technical Field
The present invention relates to a resin composition comprising an epoxy resin. Further, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device each obtained by using the resin composition.
Background
As a technique for manufacturing a printed wiring board, a manufacturing method using a stacked (build-up) method of alternately stacking insulating layers and conductor layers is known. In a manufacturing method based on a stacking method, in general, an insulating layer is formed by curing a resin composition containing an epoxy resin (patent document 1).
In recent years, with further miniaturization, higher density, and higher frequency of signals of wiring of printed wiring boards, further reduction in the relative permittivity and dielectric loss tangent of insulating layers has been demanded. As one of the improvement methods, the use of an epoxy resin in combination with a compound containing a radical polymerizable group has been studied.
However, it has been known that when a compound containing a radical polymerizable group is used, the glass transition temperature of the cured product may be lowered. In order to prevent the decrease in the glass transition temperature, it is necessary to use a curing accelerator in addition to the compound containing a radical polymerizable group, but in the case of using a curing accelerator, the degree of curing in the pre-cured state is significantly increased, and excessive internal stress is accumulated, resulting in the problem of causing cracks due to the compound containing a radical polymerizable group.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2021-130780.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to provide a resin composition capable of obtaining a cured product with excellent crack resistance.
Means for solving the problems
In order to achieve the object of the present invention, the present inventors have made an effort to study and as a result found that: the present invention has been completed by surprisingly obtaining a cured product excellent in crack resistance by using a sterically hindered compound accompanied by a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms as (C) a curing accelerator.
Namely, the present invention includes the following;
[1] a resin composition comprising (A) an epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a curing accelerator,
wherein the component (C) comprises: (C1) A compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.
[2] The resin composition according to the above [1], wherein,
(C1) The component (C) comprises a compound shown in a formula (C),
Figure BDA0004027249520000021
[ in the above-mentioned, a method for producing a semiconductor device,
R 1 an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms;
R 2 represents a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent;
R 3 and R is 4 Each independently represents a hydrogen atom or a substituent, or R 3 And R is 4 Bonded together to form an optionally substituted aromatic ring or an optionally substituted non-aromatic ring;
the double line consisting of the dotted line and the solid line represents a single bond or a double bond ].
[3] The resin composition according to the above [2], wherein,
R 2 is a group represented by the formula (R2),
Figure BDA0004027249520000022
[ in the above-mentioned, a method for producing a semiconductor device,
x represents an alkylene group having 1 to 6 carbon atoms;
y represents a single bond, -O-, -CO-, -S-, -SO 2 -, -NH-, -COO-; -OCO- -CONH-or-NHCO-;
* Represents a bonding site ].
[4] The resin composition according to any one of the above [1] to [3], wherein the content of the component (C1) is 0.001 to 1% by mass, based on 100% by mass of the nonvolatile component in the resin composition;
[5] the resin composition according to any one of the above [1] to [4], wherein the content of the component (A) is 10 to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition;
[6] the resin composition according to any one of the above [1] to [5], wherein (D) an inorganic filler is further contained;
[7] the resin composition according to the above [6], wherein the material of the component (D) comprises a material selected from the group consisting of silica, alumina, and aluminosilicate;
[8] the resin composition according to the above [6] or [7], wherein the content of the component (D) is 70% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition;
[9] the resin composition according to any one of the above [1] to [8], wherein the resin composition further comprises (E) an epoxy resin curing agent;
[10] the resin composition according to the above [9], wherein the component (E) comprises an active ester-based curing agent;
[11] The resin composition according to the above [9] or [10], wherein the component (E) comprises a phenolic curing agent;
[12] the resin composition according to any one of the above [1] to [11], wherein a relative dielectric constant (Dk) of a cured product of the resin composition is 3.5 or less when measured at 5.8GHz and 23 ℃;
[13] the resin composition according to any one of the above [1] to [12], wherein a cured product of the resin composition has a dielectric loss tangent (Df) of 0.005 or less when measured at 5.8GHz and 23 ℃;
[14] the resin composition according to any one of the above [1] to [13], wherein a coefficient of linear thermal expansion (CTE) of a cured product of the resin composition is 25ppm/K or less in a range of 25℃to 150 ℃;
[15] the resin composition according to any one of the above [1] to [14], wherein a glass transition temperature (Tg) of a cured product of the resin composition is 150℃or higher.
[16] A cured product of the resin composition according to any one of the above [1] to [15 ];
[17] a sheet laminate comprising the resin composition according to any one of the above [1] to [15 ];
[18] a resin sheet, comprising: a support and a resin composition layer formed of the resin composition according to any one of the above [1] to [15] provided on the support;
[19] A printed wiring board comprising an insulating layer comprising a cured product of the resin composition according to any one of [1] to [15 ];
[20] a semiconductor device comprising the printed wiring board of [19 ].
ADVANTAGEOUS EFFECTS OF INVENTION
According to the resin composition of the present invention, a cured product having excellent crack resistance can be obtained.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and may be modified and implemented arbitrarily within the scope of the claims and their equivalents.
< resin composition >
The resin composition of the present invention comprises (A) an epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a curing accelerator, wherein the curing accelerator comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms. According to this resin composition, a cured product having excellent crack resistance can be obtained.
The resin composition of the present invention may contain any component in addition to (a) the epoxy resin, (B) the radical polymerizable group-containing compound, and (C) the curing accelerator. Examples of the optional components include (D) an inorganic filler, (E) an epoxy resin curing agent, (F) a thermoplastic resin, (G) other additives, and (H) an organic solvent.
The components contained in the resin composition will be described in detail below.
Epoxy resin (A)
The resin composition of the present invention contains (A) an epoxy resin. (A) The epoxy resin is a curable resin having an epoxy group equivalent of 5000g/eq or less. The epoxy resin (A) described herein is a component other than the compound containing a radical polymerizable group (B) and the thermoplastic resin (F) described below.
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.
The resin composition of the present invention preferably contains (a) 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 epoxy resin (a).
(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"). The resin composition of the present invention may contain, as the epoxy resin, only a liquid epoxy resin, or only a solid epoxy resin, or both a liquid epoxy resin and a solid epoxy resin may be contained in combination, and it is particularly preferable to contain both 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.
As the liquid epoxy resin, preferred are a glycerine type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexanedimethanol type epoxy resin, a cyclic aliphatic glycidyl ether, and an epoxy resin having a butadiene structure.
Specific examples of the liquid epoxy resin include "EX-992L" manufactured by Nagase ChemteX, YX7400 "manufactured by Mitsubishi chemical corporation, and" HP4032"," HP4032D "and" HP4032SS "manufactured by DIC corporation (naphthalene type epoxy resin); "828US", "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" (Glycerol type epoxy resin) manufactured by ADEKA Co., ltd; "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" manufactured by Nissan chemical materials Co., ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Co., ltd; "EX-991L" (epoxy resin having an alkylene oxide skeleton and a butadiene skeleton) manufactured by Nagase ChemteX Co., ltd; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daxil corporation; "ZX1658", "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) manufactured by Nissan chemical materials Co., ltd; "EG-280" manufactured by Osaka gas chemical Co., ltd. (epoxy resin containing fluorene structure); "EX-201" (Cyclic aliphatic glycidyl Ether) manufactured by Nagase ChemteX Co., ltd.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, 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 tetraphenylethane-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 Co; "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. These solid epoxy resins may be used alone in an amount of 1 or in an amount of 2 or more.
When a solid epoxy resin and a liquid epoxy resin are used in combination as the epoxy resin (a), the mass ratio thereof (solid epoxy resin: liquid epoxy resin) is preferably 10:1 to 1:50, more preferably 5:1 to 1:20, particularly preferably 2:1 to 1:10.
(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5000g/eq, more preferably 60g/eq to 2000g/eq, still more preferably 70g/eq to 1000g/eq, still more preferably 80g/eq to 500g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, still more preferably 400 to 1500. The weight average molecular weight of the resin can be measured as a value converted to polystyrene by Gel Permeation Chromatography (GPC).
The content of the epoxy resin (a) in the resin composition is not particularly limited, but is preferably 50 mass% or less, more preferably 40 mass% or less, further preferably 35 mass% or less, further more preferably 30 mass% or less, particularly preferably 25 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the (a) epoxy resin in the resin composition is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 5 mass% or more, still more preferably 10 mass% or more, particularly preferably 15 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition.
(B) Compounds containing radically polymerizable groups
The resin composition of the present invention contains (B) a compound containing a radical polymerizable group. (B) The radical polymerizable group-containing compound is a compound having 1 or more (preferably 2 or more) radical polymerizable groups in 1 molecule. (B) The compound containing a radical polymerizable group may be used alone or in combination of 1 or more than 2.
The radical polymerizable group means a group having an ethylenic unsaturated bond having radical polymerization, and examples thereof are not particularly limited, and may be exemplified by (1) an acryl group, (2) a methacryl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from vinyl groups and isopropenyl groups and optionally further substituted with an alkyl group (e.g., a vinyl phenyl group (i.e., 4-vinyl phenyl group, 3-vinyl phenyl group, 2-vinyl phenyl group), an isopropenyl phenyl group (i.e., 4-isopropenyl phenyl group, 3-isopropenyl phenyl group, 2-isopropenyl phenyl group) and the like), (6) a benzyl group substituted with a group selected from vinyl groups and isopropenyl groups and optionally further substituted with an alkyl group (e.g., a vinyl benzyl group (i.e., 4-vinylbenzyl group, 3-vinylbenzyl group, 2-isopropenyl benzyl group) and the like), (7) a maleimide group (2, 5-dihydro-2, 5-dioxo-1H-pyrrole-1-yl group) and the like.
In the first embodiment, the compound (B) containing a radical polymerizable group preferably contains a thermoplastic resin having 2 or more radical polymerizable groups (for example, a number average molecular weight of 800 or more). The thermoplastic resin is not particularly limited, and examples thereof include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetheretherketone resins, polyester resins, and the like, and in this embodiment, (B) the radical polymerizable group-containing compound contains a modified resin having 2 or more radical polymerizable groups of these resins.
In the first embodiment, (B) the compound having a radical polymerizable group is preferably a resin selected from the group consisting of a modified polyphenylene ether resin having 2 or more radical polymerizable groups and a modified polystyrene resin having 2 or more radical polymerizable groups, more preferably a modified polyphenylene ether resin having 2 or more radical polymerizable groups, particularly preferably a resin represented by the formula (B) in one embodiment.
[ chemical formula 3]
Figure BDA0004027249520000071
[ in the above-mentioned, a method for producing a semiconductor device,
R 11 and R is 12 Each independently represents an alkyl group;
R 13 、R 14 、R 21 、R 22 、R 23 and R is 24 Each independently represents a hydrogen atom or an alkyl group;
R a and R is b Each independently represents (1) an acryl group, (2) a methacryl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from vinyl groups and isopropenyl groups and optionally further substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from vinyl groups and isopropenyl groups and optionally further substituted with an alkyl group;
a represents a single bond, -C (R) c ) 2 -, -O-, -CO-; -S-, -SO-, or-SO 2 -；
R c Each independently represents a hydrogen atom or an alkyl group;
s represents 0 or 1;
t and u each independently represent an integer of 1 or more. ]. The units may be the same or different for the t unit and the u unit, respectively.
R 11 And R is 12 Each independently represents an alkyl group, and in one embodiment, is preferably methyl. R is R 13 And R is 14 Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, a hydrogen atom is preferred. R is R 21 And R is 22 Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group, more preferably a methyl group. R is R 23 And R is 24 Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.
Alkyl (group) refers to a straight, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. The alkyl group (group) is preferably an alkyl group (group) having 1 to 14 carbon atoms, more preferably an alkyl group (group) having 1 to 10 carbon atoms, and still more preferably an alkyl group (group) having 1 to 6 carbon atoms unless otherwise specified. Examples of the alkyl group (group) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, tert-pentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, tert-octyl, cyclopentyl, cyclohexyl and the like.
R a And R is b Each independently represents (1) an acryl group, (2) a methacryl group, (3) an allyl group, (4) a methallyl group, (5) a phenyl group substituted with a group selected from vinyl groups and isopropenyl groups and optionally further substituted with an alkyl group, or (6) a benzyl group substituted with a group selected from vinyl groups and isopropenyl groups and optionally further substituted with an alkyl group.
In one embodiment, R a And R is b Each independently is preferably (1) phenyl substituted with a group selected from vinyl and isopropenyl and optionally further substituted with alkyl, or (2) phenyl substituted with a group selected from vinyl and isopropenyl and optionally further substituted with alkyl Benzyl substituted with alkyl; more preferably 4-vinylphenyl, 3-vinylphenyl, 2-vinylphenyl, 4-isopropenylphenyl, 3-isopropenylphenyl, 2-isopropenylphenyl, 4-vinylbenzyl, 3-vinylbenzyl, 2-vinylbenzyl, 4-isopropenylbenzyl, 3-isopropenylbenzyl, or 2-isopropenylbenzyl; particularly preferred is 4-vinylbenzyl, 3-vinylbenzyl or 2-vinylbenzyl.
A represents a single bond, -C (R) c ) 2 -, -O-, -CO-; -S-, -SO-, or-SO 2 In one embodiment, preferably a single bond, -C (R c ) 2 -, or-O-. R is R c Each independently represents a hydrogen atom or an alkyl group, and in one embodiment, is preferably a hydrogen atom or a methyl group.
s represents 0 or 1, and in one embodiment is preferably 1.t and u each independently represent an integer of 1 or more, and in one embodiment, are preferably an integer of 1 to 200, more preferably an integer of 1 to 100.
The radical polymerizable group equivalent of the radical polymerizable group-containing compound (B) in the first embodiment is preferably 300g/eq to 2500g/eq, more preferably 400g/eq to 2000g/eq. The radical polymerizable group equivalent represents the mass of the resin (compound) corresponding to 1 equivalent of the radical polymerizable group.
The number average molecular weight of the radical polymerizable group-containing compound (B) in the first embodiment is preferably 800 to 10000, more preferably 900 to 5000. The number average molecular weight of the resin can be measured by Gel Permeation Chromatography (GPC) as a polystyrene-equivalent value.
Examples of the commercial products of the compound containing a radical polymerizable group (B) in the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" manufactured by Mitsubishi gas chemical corporation (vinylbenzyl-modified polyphenylene ether resin); and "SA9000" and "SA9000-111" made by the company of Saint Foundation Innovative plastics (SABIC Innovative Plastics) (methacrylic acid modified polyphenylene ether resin).
In a second embodiment, the (B) radical polymerizable group-containing compound includes a low molecular weight compound having 2 or more radical polymerizable groups (e.g., molecular weight less than 800). Examples of such a compound include a compound having a molecular weight of less than 800 and containing a polyfunctional (meth) acryloyl group, a compound having a molecular weight of less than 800 and containing a polyfunctional vinylphenyl group, a compound having a molecular weight of less than 800 and containing a polyfunctional allyl group, and the like.
The polyfunctional (meth) acryloyl group-containing compound having a molecular weight of less than 800 is a compound having 2 or more (meth) acryloyl groups. Examples of the polyfunctional (meth) acryloyl group-containing compounds having a molecular weight of less than 800 include 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-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like; ether-containing (meth) acrylate compounds 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, and the like; isocyanurate-containing (meth) acrylate compounds such as tris (3-hydroxypropyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and ethoxylated isocyanurate tri (meth) acrylate. Examples of the commercial products of the polyfunctional (meth) acryl-containing compounds having a molecular weight of less than 800 include: "A-DOG" (dioxane diol 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) and "KAYARAD R-604" (dioxane diol diacrylate) manufactured by Nippon chemical Co., ltd.
The polyfunctional vinylphenyl-containing compound having a molecular weight of less than 800 is a compound having 2 or more vinylphenyl groups. Examples of the polyfunctional vinylphenyl-containing compound having a molecular weight of less than 800 include 4,4' -divinylbenzene, 1, 2-bis (4-vinylphenyl) ethane, 2-bis (4-vinylphenyl) propane, and bis (4-vinylphenyl) ether.
The polyfunctional allyl group-containing compound having a molecular weight of less than 800 is a compound having 2 or more allyl groups. Examples of the polyfunctional allyl-containing compound having a molecular weight of less than 800 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-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 commercially available products of the polyfunctional allyl-containing compound having a molecular weight of less than 800 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 radical polymerizable group equivalent of the radical polymerizable group-containing compound (B) in the second embodiment is preferably 30g/eq to 400g/eq, more preferably 50g/eq to 300g/eq, still more preferably 75g/eq to 200g/eq.
The molecular weight of the radical polymerizable group-containing compound (B) in the second embodiment is preferably 100 to 700, more preferably 200 to 400, still more preferably 250 to 500.
(B) The radical polymerizable group-containing compound may be contained alone in the preferred resin of the first embodiment or in any one of the preferred compounds of the second embodiment, or 2 or more of them may be contained in combination in an arbitrary ratio.
(B) The radical polymerizable group equivalent of the radical polymerizable group-containing compound is preferably 30g/eq to 2500g/eq, particularly preferably 75g/eq to 2000g/eq.
The content of the radical polymerizable group-containing compound (B) in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less, still more preferably 5 mass% or less, particularly preferably 2 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the radical polymerizable group-containing compound (B) in the resin composition is not particularly limited, but is preferably 0.001 mass% or more, more preferably 0.01 mass% or more, still more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, particularly preferably 0.5 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition.
(C) curing accelerator
The resin composition of the present invention contains (C) a curing accelerator. (C) The curing accelerator has a function as a curing catalyst for accelerating the curing of the (a) epoxy resin.
In the resin composition of the present invention, (C) the curing accelerator comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.
The nitrogen-containing heterocyclic ring means a heterocyclic ring having at least both a carbon atom and a nitrogen atom as ring-forming atoms, and further optionally having heteroatoms other than nitrogen atoms, such as an oxygen atom and a sulfur atom, as ring-forming atoms. The nitrogen-containing heterocyclic ring may be a nitrogen-containing aromatic heterocyclic ring according to the Huckel's rule having 4p+2 electrons (p is a natural number) contained in the pi-electron system on the ring, or may be a nitrogen-containing non-aromatic heterocyclic ring having no aromatic property on the whole ring, and in one embodiment, is preferably a nitrogen-containing aromatic heterocyclic ring. The nitrogen-containing heterocycle may be a monocyclic nitrogen-containing heterocycle, a bicyclic nitrogen-containing heterocycle, or a tricyclic nitrogen-containing heterocycle, and in one embodiment, a monocyclic nitrogen-containing heterocycle is preferable. In one embodiment, the nitrogen-containing heterocycle is preferably 4 to 14 membered, more preferably 5 to 10 membered. Preferable specific examples of the nitrogen-containing heterocyclic ring include monocyclic nitrogen-containing aromatic heterocyclic rings such as pyrrole ring, imidazole ring, pyrazole ring, triazole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,2, 3-triazine ring, 1,2, 4-triazine ring, and 1,3, 5-triazine ring; a bicyclic nitrogen-containing aromatic heterocycle such as an indole ring, an isoindole ring, a benzimidazole ring, and an indazole ring; a monocyclic nitrogen-containing non-aromatic heterocycle such as a pyrrolidine ring, an imidazolidine ring, an imidazoline ring, a pyrazolidine ring, a pyrazoline ring, an oxazolidine ring, an oxazoline ring, a thiazolidine ring, or a thiazoline ring; the bicyclic nitrogen-containing non-aromatic heterocycle such as indoline ring and dihydrobenzimidazole ring is preferably an imidazole ring or an imidazoline ring, particularly preferably an imidazole ring.
The hydrocarbon group means a monovalent group having only a carbon atom and a hydrogen atom as constituent atoms, and may have a linear structure, a branched structure, and/or a cyclic structure, and may be a group containing no aromatic ring or a group containing an aromatic ring. Examples of the hydrocarbon group having 7 or more carbon atoms include an alkyl group having 7 or more carbon atoms, an alkenyl group having 7 or more carbon atoms, and the like.
Alkyl groups having 7 or more carbon atoms refer to straight, branched and/or cyclic monovalent aliphatic saturated hydrocarbon groups having 7 or more carbon atoms. The carbon number of the alkyl group having 7 or more is preferably 7 to 30, more preferably 7 to 20, still more preferably 8 to 15, particularly preferably 9 to 13. The alkyl group having 7 or more carbon atoms is preferably a linear alkyl group having 7 or more carbon atoms. Examples of the alkyl group having 7 or more carbon atoms include heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl.
Alkenyl of 7 or more carbon atoms refers to a straight, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon radical of 7 or more carbon atoms having at least 1 carbon-carbon double bond. The alkenyl group having 7 or more carbon atoms preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, still more preferably 8 to 15 carbon atoms, particularly preferably 9 to 13 carbon atoms. The alkenyl group having 7 or more carbon atoms is preferably a linear alkenyl group having 7 or more carbon atoms. Examples of the alkenyl group having 7 or more carbon atoms include heptenyl (e.g., 6-heptenyl), octenyl (e.g., 7-octenyl), nonenyl (e.g., 8-nonenyl), decenyl (e.g., 9-decenyl), undecenyl (e.g., 10-undecenyl), dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, and the like.
(C1) The component (A) is preferably a nitrogen-containing heterocycle wherein a carbon atom is replaced with a hydrocarbon group having 7 or more carbon atoms. The hydrocarbon group having 7 or more carbon atoms in the nitrogen-containing heterocycle is preferably 1 or 2, particularly preferably 1, in 1 molecule. (C1) The component (a) may optionally have any substituent other than a hydrocarbon group having 7 or more carbon atoms on the nitrogen-containing heterocycle.
In one embodiment, the component (C1) preferably contains a compound represented by the formula (C).
[ chemical formula 4]
Figure BDA0004027249520000121
[ in the above-mentioned, a method for producing a semiconductor device,
R 1 an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms;
R 2 represents a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent;
R 3 and R is 4 Each independently represents a hydrogen atom or a substituent, or R 3 And R is 4 Are bonded together to formForming an optionally substituted aromatic ring or an optionally substituted non-aromatic ring;
the double line consisting of a dotted line and a solid line represents a single bond or a double bond. ].
R 1 An alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms; in one embodiment, it is preferably an alkyl group having 7 to 30 carbon atoms or an alkenyl group having 7 to 30 carbon atoms; more preferably an alkyl group having 7 to 20 carbon atoms or an alkenyl group having 7 to 20 carbon atoms; more preferably an alkyl group having 8 to 15 carbon atoms or an alkenyl group having 8 to 15 carbon atoms; more preferably an alkyl group having 9 to 13 carbon atoms or an alkenyl group having 9 to 13 carbon atoms; undecyl is particularly preferred.
R 2 Represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted aryl group, or an optionally substituted heteroaryl group.
Alkenyl (group) refers to straight, branched and/or cyclic monovalent aliphatic unsaturated hydrocarbon groups having at least 1 carbon-carbon double bond. Unless otherwise specified, the alkenyl group (group) is preferably an alkenyl group (group) having 2 to 14 carbon atoms, more preferably an alkenyl group (group) having 2 to 10 carbon atoms, and still more preferably an alkenyl group (group) having 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl group, propenyl group (allyl group, 1-propenyl group, isopropenyl group), butenyl group (1-butenyl group, crotyl group, methallyl group, isocrotonyl group, etc.), pentenyl group (1-pentenyl group, etc.), hexenyl group (1-hexenyl group, etc.), heptenyl group (1-heptenyl group, etc.), octenyl group (1-octenyl group, etc.), cyclopentenyl group (2-cyclopentenyl group, etc.), cyclohexenyl group (3-cyclohexenyl group, etc.), etc.
Aryl (group) refers to a monovalent group in which only 1 hydrogen atom of an aromatic carbocyclic ring having a carbon atom as a ring-forming atom has been removed. The aryl group (group) is preferably an aryl group (group) having 6 to 14 carbon atoms unless otherwise specified, and particularly preferably an aryl group (group) having 6 to 10 carbon atoms. Examples of the aryl group include phenyl, 1-naphthyl and 2-naphthyl.
Heteroaryl is a monovalent group obtained by removing 1 hydrogen atom of an aromatic heterocycle having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring-forming atom in addition to a carbon atom. Unless otherwise specified, heteroaryl is preferably a 5-to 14-membered heteroaryl, particularly preferably a 5-to 10-membered heteroaryl. Examples of heteroaryl groups include furyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, imidazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl (e.g., 1,3, 5-triazin-2-yl) and the like.
As R 2 The "substituent" of the alkyl group and alkenyl group in (a) is not particularly limited, and examples thereof include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, -R ', -OR ', -COR ', -SR ', -SOR ', -SO 2 R、-NHR、-NR 2 、-COOR、-OCOR、-CONHR、-CONR 2 NHCOR, etc., as R 2 The "substituent" of the aryl group and heteroaryl group in (a) is not particularly limited, and examples thereof include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, -R, -OR, -COR, -SR, -SOR, -SO 2 R、-NHR、-NR 2 、-COOR、-OCOR、-CONHR、-CONR 2 -NHCOR, etc. R 'represents (1) an aryl group optionally substituted with a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, an alkyl group, an alkenyl group, an aryl-alkyl group (an alkyl group substituted with 1 or more aryl groups), an alkyl-aryl group (an aryl group substituted with 1 or more alkyl groups), an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group, or (2) an aryl group optionally substituted with a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, an alkyl group, an alkenyl group, an aryl-aryl group, an alkyl-oxy group, an alkenyl-oxy group, and an aryl-oxy group, R represents the above (2), (3) in R' in the foregoing (1), an alkyl group optionally substituted with a group selected from the group consisting of a halogen atom, a nitro group, a cyano group, an hydroxyl group, an amino group, an alkyl group, an alkenyl group, an aryl group, an alkenyl-oxy group, an alkenyl group, and an alkenyl group, an alkenyl group.
In one embodiment, R 2 Preferably an optionally substituted alkyl group or an optionally substituted alkenyl group; more preferably an optionally substituted alkyl group; further preferably of the formula (R2)The radicals shown.
[ chemical formula 5]
Figure BDA0004027249520000131
[ in the above-mentioned, a method for producing a semiconductor device,
x represents an alkylene group having 1 to 6 carbon atoms;
y represents a single bond, -O-, -CO-, -S-, -SO 2 -, -NH-, -COO-; -OCO- -CONH-or-NHCO-; and represents a bonding site.]. By letting R 2 The group represented by the formula (R2) can raise the pH of the resin composition and promote the curing of the epoxy resin.
X represents an alkylene group having 1 to 6 carbon atoms: in one embodiment, an alkylene group having 1 to 3 carbon atoms is preferable; particularly preferably-CH 2 -CH 2 -。
Alkylene refers to a straight, branched, and/or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group having 1 to 6 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 6 carbon atoms include-CH 2 -、-CH 2 -CH 2 -、-CH(CH 3 )-、-CH 2 -CH 2 -CH 2 -、-CH 2 -CH(CH 3 )-、-CH(CH 3 )-CH 2 -、-C(CH 3 ) 2 -and the like.
Y represents a single bond, -O-, -CO-, -S-, -SO 2 -, -NH-, -COO-; -OCO- -CONH-, or-NHCO-; in one embodiment, a single bond is preferred.
R 3 And R is 4 Each independently represents a hydrogen atom or a substituent, or R 3 And R is 4 Bonded together to form an optionally substituted aromatic ring or an optionally substituted non-aromatic ring.
The aromatic ring refers to a ring in accordance with the Huckel's rule, which contains 4p+2 electrons (p is a natural number) in the pi-electron system on the ring. The aromatic ring may be an aromatic carbocyclic ring having only carbon atoms as ring-forming atoms or an aromatic heterocyclic ring having heteroatoms such as oxygen atoms, nitrogen atoms, sulfur atoms, and the like as ring-forming atoms in addition to carbon atoms. In one embodiment, the aromatic ring is preferably a 5-14 membered aromatic ring, more preferably a 6-14 membered aromatic ring, and even more preferably a 6-10 membered aromatic ring. Preferred specific examples of the aromatic ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, etc., more preferably benzene ring or naphthalene ring, particularly preferably benzene ring.
The non-aromatic ring means a ring other than an aromatic ring in which the entire ring has an aromatic nature. The non-aromatic ring may be: a non-aromatic carbocyclic ring having only carbon atoms as ring-forming atoms; or a non-aromatic heterocyclic ring having a carbon atom and having a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom or the like as a ring-forming atom. The non-aromatic ring is preferably a 3-to 21-membered non-aromatic ring, more preferably a 4-to 17-membered non-aromatic ring, and still more preferably a 5-to 14-membered non-aromatic ring. Preferable specific examples of the non-aromatic ring include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cyclopentadiene ring, a 1, 3-cyclohexadiene ring, and a 1, 4-cyclohexadiene ring.
As R 3 And R is 4 "substituent" of (C) and R 3 And R is 4 Examples of the "substituent" of the aromatic ring and the non-aromatic ring to be formed include R 2 The same group as the "substituent" of the aryl and heteroaryl groups.
In one embodiment, R 3 And R is 4 Each independently is preferably a hydrogen atom or a substituent; more preferably a hydrogen atom or an alkyl group; particularly preferred is a hydrogen atom.
The double line consisting of a dotted line and a solid line represents a single bond or a double bond; in one embodiment, a double bond is preferred.
Specific examples of the component (C1) include 2, 4-diamino-6- [2- (2-undecyl-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine and the like.
The content of the component (C1) in the resin composition is not particularly limited, but is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, still more preferably 0.01 mass% or more, particularly preferably 0.03 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition. The upper limit of the content of the component (C1) in the resin composition is not particularly limited, but is preferably 5 mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less, particularly preferably 0.1 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The content of the component (C1) in the resin composition is preferably 10 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 50 mass% or more, based on 100 mass% of the total amount of the curing accelerators (C) in the resin composition.
In the resin composition of the present invention, (C) the curing accelerator may contain (C2) a curing accelerator other than the (C1) component.
Examples of the component (C2) include imidazole-based curing accelerators other than the component (C1), amine-based curing accelerators other than the component (C1), phosphorus-based curing accelerators other than the component (C1), urea-based curing accelerators other than the component (C1), guanidine-based curing accelerators other than the component (C1), and metal-based curing accelerators other than the component (C1). (C) The curing accelerator is preferably a curing accelerator selected from imidazole curing accelerators other than the component (C1) and amine curing accelerators other than the component (C1), and particularly preferably an amine curing accelerator other than the component (C1). (C) The curing accelerator may be used alone or in combination of at least 2 kinds.
Examples of the imidazole-based curing accelerator other than the component (C1) 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-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 '-methylimidazole- (1') ] -ethyl-s triazine, 2, 4-diamino-6- [2 '-undecylimidazole ] -ethyl-s triazine, and 2, 4' -diethyl-2-ethylimidazole-trimellitate Imidazole compounds such as 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and adducts of imidazole compounds with epoxy resins.
As the imidazole-based curing accelerator other than the component (C1), commercially available ones may be used, and examples thereof include "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Mitsubishi chemical corporation, and "P200-H50" manufactured by Mitsubishi chemical corporation.
Examples of the amine-based curing accelerators other than the component (C1) 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 other than the component (C1), commercially available ones may be used, and examples thereof include "MY-25" manufactured by Weisu Fine chemistry Co.
Examples of the phosphorus-based curing accelerator other than the component (C1) 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-methylbenzophenolate, and di-t-butylmethylphosphonium 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 reactants; 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-pyridyl phosphine, 1, 2-bis (diphenyl) ethane, 1, 3-bis (diphenyl) propane, bis (2, 2' -diphenyl) phosphine, bis (diphenyl) phosphine, etc.
Examples of the urea-based curing accelerator other than the component (C1) 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 other than the component (C1) 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, and 1- (o-tolyl) biguanide.
Examples of the metal curing accelerator other than the component (C1) include metal, organic metal complexes or organic metal salts of cobalt, copper, zinc, iron, nickel, manganese, tin, and the like. Specific examples of the organometallic complex include cobalt (II) acetylacetonate, organic cobalt complexes such as cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, organic zinc complexes such as zinc (II) acetylacetonate, organic iron complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
The content of the curing accelerator (C) in the resin composition is not particularly limited, but is preferably 0.0001 mass% or more, more preferably 0.001 mass% or more, still more preferably 0.01 mass% or more, particularly preferably 0.05 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition. The upper limit of the content of the curing accelerator (C) in the resin composition is not particularly limited, but is preferably 5 mass% or less, more preferably 1 mass% or less, still more preferably 0.5 mass% or less, particularly preferably 0.2 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition.
Inorganic filler (D)
The resin composition of the present invention may contain (D) an inorganic filler as an optional component. (D) The inorganic filler is contained in the resin composition in the form of particles.
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, aluminosilicate, 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, zirconium phosphotungstate, and the like. (D) The material of the inorganic filler is preferably a material selected from the group consisting of silica, alumina, and aluminosilicate, and particularly preferably silica. (D) The inorganic filler may be 1 kind of inorganic filler, or 2 or more kinds of inorganic fillers may be combined at an arbitrary ratio.
(D) The inorganic filler may be composed of only (D1) a hollow inorganic filler, may be composed of only (D2) a solid inorganic filler, or may be composed of both (D1) a hollow inorganic filler and (D2) a solid inorganic filler. (D) The inorganic filler is preferably composed of both (D1) a hollow inorganic filler and (D2) a solid inorganic filler.
(D1) The hollow inorganic filler may be an inorganic filler containing single hollow particles having only 1 hollow in the particle, or an inorganic filler containing multi-hollow particles having a plurality of hollow in the particle, or both.
The hollow inorganic filler (D1) has an average porosity of more than 0% by volume, preferably 1% by volume or more, more preferably 5% by volume or more, still more preferably 10% by volume or more, particularly preferably 15% by volume or more. (D1) The upper limit of the average porosity of the hollow inorganic filler is not particularly limited, but is preferably 90% by volume or less, more preferably 85% by volume or less.
The average porosity P (volume%) of the inorganic filler is calculated as the total volume of 1 or 2 or more pores existing in the interior of the particles relative to the total volume of the particlesThe volume reference ratio (total volume of voids/volume of particles) of the whole volume of the particles with the outer surface as a reference is defined, and for example, a measured value D of the actual density of the inorganic filler can be used M (g/cm 3 ) And theoretical value D of the mass density of the material forming the inorganic filler material T (g/cm 3 ) Calculated by the following formula (I).
[ mathematics 1]
Figure BDA0004027249520000181
The actual density of the inorganic filler can be measured, for example, using a true density measuring device. Examples of the true density measuring apparatus include ULTRAPYCOMETER 1000 manufactured by QUANTACHOME, inc. As the measurement gas, for example, nitrogen gas is used.
(D1) The hollow inorganic filler is preferably a hollow inorganic filler selected from the group consisting of spherical hollow silica, spherical hollow alumina, and spherical hollow aluminosilicate. (D1) The hollow inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds in any ratio.
(D1) The average particle diameter of the hollow inorganic filler is preferably 10 μm or less, more preferably 5 μm or less, and still more preferably 3 μm or less. (D1) The lower limit of the average particle diameter of the hollow inorganic filler is not particularly limited, but 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.
The average particle size of the inorganic filler material can be determined by a laser diffraction-scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced by a laser diffraction scattering type particle size distribution measuring apparatus on a volume basis, and the median particle size can be measured as the average particle size. As a measurement sample, a sample obtained by weighing 100mg of an inorganic filler and 10g of methyl ethyl ketone into a vial and dispersing 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 used 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), and the average particle size was calculated from the obtained particle size distribution as the median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
(D1) The specific surface area of the hollow inorganic filler is not particularly limited, but is preferably 0.1m 2 Preferably at least 0.5m 2 Preferably at least 1m 2 Preferably at least 3m 2 And/g. (D1) The upper limit of the specific surface area of the hollow inorganic filler is not particularly limited, but is preferably 100m 2 Preferably less than or equal to/g, more preferably 70m 2 Preferably less than or equal to/g, more preferably 50m 2 Preferably less than/g, particularly preferably 40m 2 And/g or less. The specific surface area of the inorganic filler can be obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech, ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.
Examples of the commercial products of the hollow inorganic filler (D1) include "BA-S" (average particle size 2.6 μm, porosity 25 vol%) made by the daily volatile catalyst formation company, "LHP-208" (average particle size 0.5 μm, porosity 50 vol%) made by the Ube Exsymo company, "DLSB-001" (average particle size 0.23 μm, porosity 20 vol%) made by the Dacron chemical company, "MG-005" (average particle size 1.6 μm, porosity 80 vol%) made by the Taiheiyo-ceramic company, and the like.
From the viewpoint of improving moisture resistance and dispersibility, (D1) the hollow inorganic filler is preferably treated with a surface treating agent. Examples of the surface treatment agent include: fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, alkoxysilanes, organosilane-nitrogen compounds, titanate coupling agents, and the like. The surface treatment agent may be used alone or in combination of 2 or more kinds.
Examples of the commercial products of the surface treatment agent include "KBM403" manufactured by Xinshi chemical industry Co., ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" manufactured by Xinshi chemical industry Co., ltd. (3-mercaptopropyl trimethoxysilane), "KBE903" manufactured by Xinshi chemical industry Co., ltd. (3-aminopropyl triethoxysilane), "KBM573" manufactured by Xinshi chemical industry Co., ltd. (N-phenyl-3-aminopropyl trimethoxysilane), "SZ-31" manufactured by Xinshi chemical industry Co., ltd. (hexamethyldisilazane), "KBM103" manufactured by Xinshi chemical industry Co., ltd. (phenyl trimethoxysilane), "KBM-4803" manufactured by Xinshi chemical industry Co., ltd. (long-chain epoxy silane coupling agent), and "KBM 7103" manufactured by Xinshi chemical industry Co., ltd. (3, 3-trifluoropropyl trimethoxysilane).
From the viewpoint of improving the dispersibility of the hollow inorganic filler (D1), the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, the hollow inorganic filler (D1) 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.
The degree of surface treatment with the surface treatment agent can be evaluated by (D1) the amount of carbon per unit surface area of the hollow inorganic filler. From the viewpoint of improving the dispersibility of the hollow inorganic filler (D1), the carbon amount per unit surface area of the hollow inorganic filler (D1) is preferably 0.02mg/m 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 suppressing the rise in melt viscosity of the resin composition and in melt viscosity in sheet form, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The concentration of the component (A) is more preferably 0.5mg/m 2 The following is given.
In terms of suppressing the relative dielectric constant to a lower level, the content (mass%) of the hollow inorganic filler (D1) in the inorganic filler (D) is preferably 10 mass% or more, more preferably 20 mass% or more, and even more preferably 30 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition. (D) The upper limit of the content (mass%) of the hollow inorganic filler in (D1) in the inorganic filler is not particularly limited, but the non-volatile component in the resin composition may be preferably 90 mass% or less, more preferably 80 mass% or less, still more preferably 75 mass% or less, still more preferably 70 mass% or less, particularly preferably 60 mass% or less, based on 100 mass%.
(D2) The average porosity of the solid inorganic filler material was 0% by volume.
(D2) The solid inorganic filler is preferably a solid inorganic filler selected from the group consisting of spherical solid silica, spherical solid alumina, and spherical solid aluminosilicate. (D2) The solid inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds in any ratio.
(D2) The average particle diameter of the solid inorganic filler is preferably 5 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.6 μm or less. (D2) The lower limit of the average particle diameter of the solid inorganic filler is not particularly limited, but 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.
(D2) The specific surface area of the solid inorganic filler is not particularly limited, but is preferably 0.1m 2 Preferably at least 0.5m 2 Preferably at least 1m 2 Preferably at least 3m 2 And/g. (D2) The upper limit of the specific surface area of the solid inorganic filler is not particularly limited, but is preferably 100m 2 Preferably less than or equal to/g, more preferably 70m 2 Preferably less than or equal to/g, more preferably 50m 2 Preferably less than/g, particularly preferably 40m 2 And/g or less.
Examples of the commercial products of the solid inorganic filler (D2) include "SP60-05" and "SP507-05" manufactured by Nissan iron chemical materials Co., ltd; "YC100C", "YA050C-MJE", "YA010C" manufactured by Yadu MAX Co., ltd; "UFP-30" manufactured by DENKA corporation; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Deshan corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by Yakuma Co., ltd; "DAW-03", "FB-105FD", etc. manufactured by DENKA corporation.
From the viewpoint of improving moisture resistance and dispersibility, (D2) the solid inorganic filler is preferably treated with a surface treating agent.
From the viewpoint of improving the dispersibility of the solid inorganic filler (D2), the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, the surface treatment is preferably performed with 0.2 to 5 mass% of the surface treatment agent, more preferably with 0.2 to 3 mass% of the surface treatment agent, and still more preferably with 0.3 to 2 mass% of the surface treatment agent, based on 100 mass% of the solid inorganic filler (D2).
The degree of surface treatment by the surface treatment agent can be evaluated by (D2) the amount of carbon per unit surface area of the solid inorganic filler. From the viewpoint of improving the dispersibility of the (D2) solid inorganic filler, the carbon amount per unit surface area of the (D2) solid inorganic filler is preferably 0.02mg/m 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 the rise of the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The concentration of the component (A) is more preferably 0.5mg/m 2 The following is given.
When the nonvolatile content in the resin composition is set to 100% by mass, the content (mass%) of the (D) inorganic filler in the resin composition is, for example, 0% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass or more, and particularly preferably 70% by mass or more. The upper limit of the content (mass%) of the inorganic filler in the resin composition is not particularly limited, but the non-volatile component in the resin composition may be preferably 90 mass% or less, more preferably 85 mass% or less, and still more preferably 80 mass% or less, based on 100 mass%.
When the nonvolatile content in the resin composition is set to 100% by volume, the content (vol%) of the (D) inorganic filler in the resin composition is, for example, 0% by volume or more, 10% by volume or more, preferably 20% by volume or more, more preferably 30% by volume or more, still more preferably 40% by volume or more, still more preferably 50% by volume or more, and particularly preferably 60% by volume or more. The upper limit of the content (vol%) of the inorganic filler in the resin composition is not particularly limited, but the content of the non-volatile component in the resin composition may be preferably 80 vol% or less, more preferably 75 vol% or less, and further preferably 70 vol% or less, based on 100 vol%.
Epoxy resin curing agent
The resin composition of the present invention may contain (E) an epoxy resin curing agent as an optional component. (E) The epoxy resin curing agent may have a function of reacting with (a) the epoxy resin to cure it. (E) The epoxy resin curing agent may be used alone or in combination of 2 or more kinds. The epoxy resin curing agent (E) described herein is a component other than the thermoplastic resin (F) described below.
The epoxy resin curing agent (E) is not particularly limited, and examples thereof include an active ester curing agent, a phenol curing agent, a carbodiimide curing agent, an acid anhydride curing agent, an amine curing agent, a benzoxazine curing agent, a cyanate curing agent, and a thiol curing agent. In one embodiment, the epoxy resin curing agent (E) preferably contains 1 or more epoxy resin curing agents selected from the group consisting of active ester curing agents, phenolic curing agents, and cyanate ester curing agents, and more preferably contains 1 or more epoxy resin curing agents selected from the group consisting of active ester curing agents and phenolic curing agents. In one embodiment, the (E) epoxy resin curing agent particularly preferably contains an active ester curing agent from the viewpoint of controlling the dielectric loss tangent to a lower value. In one embodiment, the (E) epoxy resin curing agent particularly preferably contains a phenolic curing agent from the viewpoint of further improving curability.
As the active ester-based 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, are generally preferably used. The active ester compound is preferably a compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound. Particularly, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferable, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or the naphthol compound include hydroquinone, resorcinol, bisphenol a, bisphenol F, bisphenol S, phenolphthalein, 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, trihydroxybenzone, tetrahydroxybenzophenone, phloroglucinol, and novolac (phenol novolac). The "dicyclopentadiene type phenol compound" refers to a phenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.
The active ester-based curing agent is preferably a dicyclopentadiene-type active ester compound, an active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a novolac resin, or an active ester compound containing a benzoyl compound of a novolac resin, and among these, at least one selected from the dicyclopentadiene-type active ester compound and the naphthalene-type active ester compound is more preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable.
As commercial products of the active ester curing agent, active ester compounds containing dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC Co.); examples of the active ester compound having a naphthalene structure include "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Co.); examples of the phosphorus-containing active ester compound include "EXB9401" (manufactured by DIC Co.); examples of the active ester compound of the acetyl compound of the novolac resin include "DC808" (manufactured by mitsubishi chemical company); examples of the active ester compound of the benzoyl compound of the novolac resin include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester compound having a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by AIR & WATER Co., ltd.).
As the phenolic curing agent, a phenolic curing agent having a phenolic structure (novolac structure) is preferable from the viewpoints of heat resistance and water resistance. In addition, from the viewpoint of adhesion to an adherend, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, a novolac resin (phenol novolac resin) containing a triazine skeleton is preferable. Specific examples of the phenol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals, inc., and "NHN", "CBN", "GPH", 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", "2090", "KA-1160" manufactured by DIC, etc.
Examples of the carbodiimide-based curing agent include curing agents having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule, and examples thereof 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 ].
Examples of the commercial products of the carbodiimide curing agent include: "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nisshinoki chemical Co., ltd; "Stabaxol P", "Stabaxol P400", "Hycasyl 510", 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-furyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic 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-furyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (dehydrated trimellitate), styrene-maleic acid resin copolymerized from styrene, and the like. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", mitsubishi chemical corporation, "YH-306", "YH-307", hitachi chemical corporation, "HN-2200", "HN-5500", and "EF-30", "EF-40", "EF-60" and "EF-80" of Cray Valley.
The amine-based curing agent may be a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among these, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. As a specific example of the amine-based curing agent, examples thereof 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. As the amine-based curing agent, commercially available products can be used, and examples thereof include "SEIKACURE-S" manufactured by SEIKA corporation, and "KAYABOND C-200S" manufactured by Japanese chemical company, KAYABOND C-100"," KAYAHARD A-A "," KAYAHARD A-B "," KAYAHARD A-S ", and" Epicure W "manufactured by Mitsubishi chemical corporation.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE chemical company; "HFB2006M" manufactured by Showa Polymer Co., ltd; "P-d", "F-a", etc. manufactured by the chemical industry Co., ltd.
Examples of the cyanate-based curing agent include bisphenol a dicyanate, polyphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 2-functional cyanate resins such as 4,4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylenediphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanate 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 phenyl) ether, multifunctional cyanate resins derived from phenol novolac resins and cresol novolac resins, and partially triazinized prepolymers of these cyanate resins. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by Lonza japan (both are phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol a dicyanate is triazinized into a trimer).
Examples of the thiol-based curing agent include: trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and the like.
(E) The equivalent weight of the reactive group of the epoxy resin 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 equivalent of the reactive group is the mass of the (E) epoxy resin curing agent per 1 equivalent of the reactive group.
When the active ester-based curing agent is contained as the epoxy resin curing agent (E), the content of the active ester-based curing agent in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, particularly preferably 8% by mass or more, from the viewpoint of suppressing the dielectric loss tangent to be lower, when the nonvolatile content in the resin composition is 100% by mass. In addition, from the viewpoint of suppressing the dielectric loss tangent to a lower level, the content of the active ester-based curing agent in the (E) epoxy resin curing agent is preferably 10 mass% or more, more preferably 30 mass% or more, still more preferably 40 mass% or more, particularly preferably 50 mass% or more, based on 100 mass% of the total amount of the (E) epoxy resin curing agent in the resin composition.
When the phenol curing agent is contained as the epoxy resin curing agent (E), the content of the phenol curing agent in the resin composition is preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 1.5 mass% or more, particularly preferably 1.7 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition, from the viewpoint of further improving curability.
The content of the (E) epoxy resin curing agent in the resin composition is not particularly limited, but is preferably 30 mass% or less, more preferably 25 mass% or less, further preferably 20 mass% or less, further preferably 15 mass% or less, particularly preferably 13 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the (E) epoxy resin curing agent in the resin composition is not particularly limited, but may be preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 5 mass% or more, still more preferably 8 mass% or more, and particularly preferably 10 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition.
Thermoplastic resin (F)
The resin composition of the present invention may contain (F) a thermoplastic resin as an optional component. (F) The thermoplastic resin is a component other than the epoxy resin (a) described above.
Examples of the thermoplastic resin (F) include: polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and the like. In one embodiment, (F) the thermoplastic resin preferably contains a thermoplastic resin selected from polyimide resins and phenoxy resins, more preferably contains a phenoxy resin. (F) The thermoplastic resin may be used alone or in combination of 2 or more.
Specific examples of the polyimide resin include "SLK-6100" manufactured by the more chemical industry Co., ltd., and "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by New Japan physical and chemical Co., ltd.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of frameworks selected from bisphenol a frameworks, bisphenol F frameworks, bisphenol S frameworks, bisphenol acetophenone frameworks, phenol frameworks, biphenyl frameworks, fluorene frameworks, dicyclopentadiene frameworks, norbornene frameworks, naphthalene frameworks, anthracene frameworks, adamantane frameworks, terpene frameworks, and trimethylcyclohexane frameworks. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
Specific examples of the phenoxy resin include: "1256" and "4250" both made by Mitsubishi chemical corporation (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; "YX7200B35", "YL7500BH30", "YX6954BH30", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc. manufactured by Mitsubishi chemical corporation.
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: "electrochemical butyral 4000-2", "electrochemical butyral 5000-A", "electrochemical butyral 6000-C", "electrochemical butyral 6000-EP" manufactured by the electric chemical industry company; 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.
The polybutadiene resin includes, for example: hydrogenated polybutadiene skeleton-containing resins, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, polyphenylene ether-polybutadiene resins, and the like.
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.
The polycarbonate resin may be: hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, and the like. Specific examples of the polycarbonate resin include "FPC0220" manufactured by Mitsubishi gas chemical corporation, "T6002" and "T6001" manufactured by Asahi chemical corporation (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 dimethyl terephthalate resin.
From the viewpoint of further improving the film formability, the weight average molecular weight (Mw) of the thermoplastic resin (F) is preferably 5000 or more, more preferably 8000 or more, still more preferably 10000 or more, particularly preferably 20000 or more, preferably 100000 or less, more preferably 70000 or less, still more preferably 60000 or less, particularly preferably 50000 or less.
The content of the thermoplastic resin (F) in the resin composition is not particularly limited, but may be preferably 20 mass% or less, more preferably 15 mass% or less, still more preferably 10 mass% or less, still more preferably 5 mass% or less, and particularly preferably 2 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the thermoplastic resin (F) in the resin composition is not particularly limited, but is, for example, 0 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, still more preferably 0.1 mass% or more, still more preferably 0.5 mass% or more, and particularly preferably 0.7 mass% or more, based on 100 mass% of the nonvolatile component in the resin composition.
(G) other additives
The resin composition of the present invention may further contain any additive. Examples of such additives 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-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. (G) The other additives may be used alone or in combination of two or more kinds in any ratio. If the person skilled in the art is concerned, the content of the other additives (G) can be appropriately set.
Organic solvent (H)
The resin composition of the present invention may further contain an optional organic solvent. As the organic solvent (H), a known solvent may be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (H) 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 (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. (H) The organic solvent may be used alone or in combination of two or more kinds in any ratio.
The content of the organic solvent (H) in the varnish-like resin composition before drying is not particularly limited, but is, for example, 40 mass% or less, 30 mass% or less, preferably 20 mass% or less, more preferably 10 mass% or less, still more preferably 8 mass% or less, and particularly preferably 6 mass% or less, based on 100 mass% of the total components in the resin composition. The content of the organic solvent (H) in the resin composition after drying to form the resin composition layer in the resin sheet is not particularly limited, but is preferably 5 mass% or less, more preferably 3 mass% or less, still more preferably 2 mass% or less, particularly preferably 1 mass% or less, based on 100 mass% of the total components in the resin composition.
Method for producing resin composition
The resin composition of the present invention can be produced, for example, by: in an optional preparation vessel, (A) an epoxy resin, (B) a radical polymerizable group-containing compound, (C) a curing accelerator, optionally (D) an inorganic filler, optionally (E) an epoxy resin curing agent, optionally (F) a thermoplastic resin, optionally (G) other additives, and optionally (H) an organic solvent are added in an optional order and/or simultaneously with a part or all and mixed. In addition, the temperature may be set appropriately during the process of adding and mixing the components, and heating and/or cooling may be performed temporarily or constantly. In addition, during the addition and mixing process, or after the process, the resin composition may be stirred or oscillated to be uniformly dispersed, for example, using a stirring device or an oscillating device of a mixer or the like. The defoaming may be performed under low pressure such as vacuum while stirring or shaking.
< Properties of resin composition >
The resin composition of the present invention comprises (A) an epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a curing accelerator, wherein the curing accelerator comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms. According to this resin composition, a cured product having excellent crack resistance can be obtained.
The cured product of the resin composition of the present invention may have a feature that it is possible to suppress the occurrence of cracks after the desmutting treatment (roughening treatment). Therefore, in one embodiment, after the circuit board is manufactured and the stain-removing treatment is performed as in test example 3 below, the number of cracks may be preferably less than 15% (15% or less), particularly preferably less than 5% (5% or less) when 100 copper pads of the circuit board are observed.
In one embodiment, the cured product of the resin composition of the present invention may have a characteristic of low coefficient of linear thermal expansion (CTE). Therefore, in one embodiment, the linear thermal expansion Coefficient (CTE) of the cured product measured as in test example 1 below is in the range from 25℃to 150℃and preferably 40ppm/K or less, more preferably 35ppm/K or less, still more preferably 30ppm/K or less, still more preferably 25ppm/K or less, particularly preferably 22ppm/K or less. The lower limit of the coefficient of linear thermal expansion (CTE) is not particularly limited, and may be 1ppm/K or more.
In one embodiment, the cured product of the resin composition of the present invention may have a characteristic of higher glass transition temperature (Tg). Accordingly, in one embodiment, the glass transition temperature (Tg) when measured as in test example 1 below may be preferably 120 ℃ or higher, more preferably 130 ℃ or higher, still more preferably 140 ℃ or higher, still more preferably 145 ℃ or higher, particularly preferably 150 ℃ or higher.
In one embodiment, the cured product of the resin composition of the present invention may have a characteristic of lower dielectric loss tangent (Df). Accordingly, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8GHz and 23 ℃ as in test example 2 below may be preferably 0.010 or less, more preferably 0.009 or less, still more preferably 0.008 or less, still more preferably 0.007 or less, still more preferably 0.006 or less, or 0.0055 or less, and particularly preferably 0.005 or less, or 0.0045 or less.
In one embodiment, the cured product of the resin composition of the present invention may have a characteristic of lower relative dielectric constant (Dk). Therefore, in one embodiment, the relative dielectric constant (Dk) of the cured product of the resin composition when measured at 5.8GHz and 23℃as in test example 2 below is not particularly limited, but is preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.7 or less, still more preferably 3.5 or less, and particularly preferably 3.3 or less.
Use of resin composition
The resin composition of the present invention can be suitably used as a resin composition for insulation use, particularly a resin composition for forming an insulating layer. Specifically, the resin composition (resin composition for forming an insulating layer for forming a conductor layer) can be suitably used as a resin composition for forming the insulating layer for forming a conductor layer (the conductor layer is formed on an insulating layer, and the conductor layer includes a rewiring layer). In addition, in the printed wiring board described later, the resin composition can be suitably used as a resin composition for forming an insulating layer of the printed wiring board (a resin composition for forming an insulating layer of the printed wiring board). The resin composition of the present invention can be used for various applications requiring 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 hole-filling resin, and a component-embedding resin.
In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as: a resin composition for a re-wiring layer forming (a resin composition for a re-wiring layer forming) as an insulating layer for forming a re-wiring layer, and a resin composition for sealing a semiconductor chip (a resin composition for sealing a semiconductor chip). In manufacturing the semiconductor chip package, 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 a 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.
In addition, since the resin composition of the present invention forms an insulating layer having excellent embedding properties for components, it can be suitably used in the case where a printed wiring board is a component-embedded circuit board.
< sheet laminate >)
The resin composition of the present invention may be used in the form of a varnish, but is industrially preferably used in the form of a sheet laminate containing the resin composition.
The sheet-like laminate is preferably a resin sheet or prepreg as shown below.
In one embodiment, a resin sheet includes a support, and a resin composition layer provided on the support, the resin composition layer being formed from the resin composition of the present invention.
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 provision of 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 usually 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.
In the case of using a film formed of a plastic material as a support, examples of the plastic material include: polyesters such as polyethylene terephthalate (hereinafter, abbreviated as "PET"), polyethylene naphthalate (hereinafter, abbreviated as "PEN") and acrylic polymers such as polycarbonate (hereinafter, abbreviated as "PC"), 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 particularly inexpensive polyethylene terephthalate is 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 support may be subjected to a matte treatment, a corona treatment, or an antistatic treatment on the surface to be joined to the resin composition layer.
Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer can be used. As the release agent for the release layer of the support with a release layer, for example, 1 or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins are exemplified. Examples of the support having a release layer include PET film having a release layer composed mainly of an alkyd resin type release agent, specifically, "SK-1", "AL-5", "AL-7" made by Leideae, and "LUMIRROR T60" made by Toli, and "Purex" made by Di people, and "Unipel" made by UNITKA.
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 within 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 selected for the support and provided on a surface of the resin composition layer not joined to the support (i.e., a surface opposite to the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, the adhesion of refuse or the like to the surface of the resin composition layer or the formation of damage can be suppressed.
The resin sheet can be produced, for example, by: the 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 the resin composition in an organic solvent to prepare a liquid (varnish-like) resin composition, and applying the liquid (varnish-like) resin composition to a support using a die coater or the like, followed by drying the same.
The organic solvent may be the same as the organic solvent described as a component 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 or blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. When a resin composition containing 30 to 60 mass% of an organic solvent is used, for example, a resin composition layer can be formed by drying at 50 to 150℃for 3 to 10 minutes, depending on the boiling point of the organic solvent in the resin composition.
The resin sheet may be wound into a roll and stored. When the resin sheet has a protective film, the protective film can be peeled off for use.
In one embodiment, the prepreg is formed by impregnating a sheet-like fibrous substrate with the resin composition of the present invention.
The sheet-like fibrous base material used in the prepreg is not particularly limited, and glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, or the like can be used as a material commonly used as a base material for the prepreg. 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, still more preferably 30 μm or less, particularly preferably 20 μm or less. The lower limit of the thickness of the sheet-like fibrous base material is not particularly limited. Typically 10 μm or more.
The prepreg can be produced by a known method such as a hot melt method or a solvent method.
The thickness of the prepreg may be in the same range as the resin composition layer in the resin sheet described above.
The sheet-like laminate of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), and can be 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 of the present invention comprises an insulating layer formed from a cured product obtained by curing the resin composition of the present invention.
The printed wiring board can be manufactured, for example, by a method including the steps (I) and (II) described below using the resin sheet described above;
(I) A step of laminating the resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate, and a step of forming an insulating layer by curing (e.g., thermally curing) the resin composition 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 insulating layers and/or conductor layers in the production of printed wiring boards are also included in the so-called "inner layer substrates" in the present invention. When the printed wiring board is a component-embedded circuit board, an inner layer board having a component embedded therein may be used.
Lamination of the inner substrate and the resin sheet can be performed, for example, by thermocompression bonding the resin sheet to 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) or a metal roller (SUS roller) or the like is 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 heat press-bonding temperature is preferably in the range of 60℃to 160℃and more preferably in the range of 80℃to 140℃and the heat press-bonding pressure is preferably in the range of 0.098MPa to 1.77MPa and more preferably in the range of 0.29MPa to 1.47MPa, and the heat press-bonding time is preferably in the range of 20 seconds to 400 seconds and more preferably in the range of 30 seconds to 300 seconds. The lamination can be 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, batch vacuum pressurized laminators, and the like.
After lamination, the laminated resin sheets can be smoothed by pressing the thermocompression bonding member from the support body side at normal pressure (atmospheric pressure), for example. The pressing conditions for the smoothing treatment may be set to the same conditions as those for the thermocompression bonding of the laminate. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be performed continuously 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 (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing condition of the resin composition layer is not particularly limited, and 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, etc., and in one embodiment, the curing temperature is preferably 120 to 240 ℃, more preferably 150 to 220 ℃, still 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 at a temperature of 50 to 120 ℃, preferably 60 to 115 ℃, more preferably 70 to 110 ℃ for at least 5 minutes, preferably 5 to 150 minutes, more preferably 15 to 120 minutes, still more preferably 15 to 100 minutes, 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. These steps (III) to (V) can 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). If necessary, the insulating layer and the conductor layer may be formed repeatedly in the steps (II) to (V), thereby forming a multilayer wiring board.
In other embodiments, the printed wiring board of the present invention 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, whereby a hole such as a through hole or a through hole can be formed in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, a 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 can be appropriately determined according to the design of the printed wiring board.
The step (IV) is a step of roughening the insulating layer. In this step (IV), generally, 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 generally 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.
The swelling liquid used in the roughening treatment is not particularly limited, and examples thereof include an alkali solution, a surfactant solution, and the like, preferably an alkali solution, and as the alkali solution, sodium hydroxide solution and potassium hydroxide solution are more preferred. 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 liquid is not particularly limited, and for example, the insulating layer may be immersed in the swelling liquid 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.
The oxidizing agent used in the roughening treatment is not particularly limited, and examples thereof 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 ambett japan.
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 ambari japan.
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 impregnate the object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 to 70 ℃ for 5 to 20 minutes.
In one embodiment, the arithmetic average roughness (Ra) of the surface of the insulating layer after the roughening treatment is not particularly limited, but 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 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 1 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 2 or more metals selected from the above group (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, from the viewpoints of versatility, cost, ease of patterning, and the like of the conductor layer formation, 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, or 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 2 or more layers of 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 the 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 using 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 vacuum lamination. The conditions for lamination may be the same as those described for 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 an 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
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
Examples of the semiconductor device include various semiconductor devices used for electric products (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, electric trains, ships, and aircraft, and the like).
Examples
The present invention will be specifically described below with reference to examples. The present invention is not limited by these examples. In the following, unless otherwise specified, "part" and "%" indicating amounts refer to "part by mass" and "% by mass", respectively. The temperature condition in the case where the temperature is not specified is room temperature (23 ℃) and the pressure condition in the case where the pressure is not specified is atmospheric pressure (1 atm).
Example 1 >
30 parts of bisphenol A type epoxy resin (828 US, manufactured by Mitsubishi chemical corporation, about 180g/eq of epoxy equivalent) and 30 parts of biphenyl type epoxy resin (NC 3000H, manufactured by Japanese chemical corporation, about 269g/eq of epoxy equivalent) were dissolved in 55 parts of solvent naphtha with stirring, and then cooled to room temperature. In this mixed solution, 280 parts of spherical silica (SO-C2, average particle diameter 0.5 μm, manufactured by mitsubishi chemical Co., ltd.) surface-treated with an aminosilane coupling agent (KBM 573, manufactured by Xinyue chemical Co., ltd.), 10 parts of a triazine skeleton-containing phenol curing agent (LA-3018-50P, manufactured by DIC chemical Co., ltd.), 14 parts of a hydroxyl equivalent, a solid content of 50% 2-methoxypropanol solution, 55 parts of an active ester compound (HPC-8000-65T, an active group equivalent of about 223, a nonvolatile content of 65 mass% toluene solution), 10 parts of a phenoxy resin (YX 6954BH30, manufactured by Mitsubishi chemical Co., ltd.), 3 parts of a vinyl compound (1:1 mixed solution of 30 mass% MEK and cyclohexanone, 3 parts of a vinyl compound (1-DOG, manufactured by Sanyo chemical Co., ltd.), 3 parts of a curing accelerator A (2, 4-diamino-6- [2- (1-undecyl) -1H-3-5-methoxy-ethyl) were mixed, and a varnish was prepared, and a high-speed spin-mixing solution was used.
(method for measuring average particle diameter of inorganic filler)
100mg of inorganic filler material and 10g of methyl ethyl ketone were weighed into a vial and dispersed by ultrasonic waves for 10 minutes. The particle size distribution of the inorganic filler was measured by a flow cell method using a laser diffraction particle size distribution measuring apparatus (LA-960 manufactured by horiba ltd.) with the wavelength of the light source used being blue and red. The average particle diameter of the inorganic filler was calculated from the obtained particle diameter distribution as the median particle diameter.
Example 2 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that the amount of the curing accelerator a (2, 4-diamino-6- [2- (2-undecyl-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine, 5% by mass solids in 2-methoxypropanol solution) was changed from 6 parts to 4 parts, and 2 parts of the curing accelerator ("DMAP", 4-dimethylaminopyridine, 5% by mass solids in MEK solution) was further mixed.
Example 3 >
A varnish-like resin composition was prepared in the same manner as in example 2 except that 30 parts of a naphthol-type epoxy resin (ESN 475V, epoxy equivalent 332g/eq, manufactured by daily iron chemical Co., ltd.) was used instead of 30 parts of a biphenyl-type epoxy resin (NC 3000H, epoxy equivalent 269g/eq, manufactured by japan chemical Co., ltd.).
Example 4 >
A varnish-like resin composition was prepared in the same manner as in example 2, except that 30 parts of a biphenyl type epoxy resin (NC 3000H, epoxy equivalent of about 269g/eq, manufactured by japan chemical corporation) was used instead of 30 parts of a biscresol type epoxy resin (YX 4000HK, epoxy equivalent of about 185g/eq, manufactured by mitsubishi chemical corporation).
Example 5 >
A varnish-like resin composition was prepared in the same manner as in example 2 except that 55 parts of an active ester compound (HPC-8000-65T, available from DIC Co., ltd., an active group equivalent of about 223, a toluene solution containing 65% by mass of nonvolatile components) was not used, and the amount of a phenol-based curing agent (LA-3018-50P, available from DIC Co., ltd., a 2-methoxypropanol solution having a hydroxyl equivalent of about 151 and a solid content of 50%) having a triazine skeleton was changed from 14 parts to 40 parts, and the amount of spherical silica (SO-C2, available from Xinyue chemical Co., ltd., an average particle diameter of 0.5 μm) surface-treated with an aminosilane-based coupling agent was changed from 280 parts to 220 parts.
Example 6 >
A varnish-like resin composition was prepared in the same manner as in example 2, except that 3 parts of an allyl group-containing benzoxazine compound (ALP-d manufactured by quassia chemical industry Co., ltd.) was used instead of 3 parts of an acrylate compound (a-DOG manufactured by neo-well chemical industry Co., ltd.).
Example 7 >
A varnish-like resin composition was prepared in the same manner as in example 2, except that 4.6 parts of a low polyphenylene ether-styrene resin (OPE-2 st 1200, no volatile matter 65% toluene solution, manufactured by mitsubishi gas chemical company) was used instead of 3 parts of an acrylate compound (a-DOG, dioxane glycol diacrylate, manufactured by new yo chemical industries, co.).
Example 8 >
A varnish-like resin composition was prepared in the same manner as in example 2 except that the amount of spherical silica (SO-C2, average particle size 0.5 μm, manufactured by Santa Clara, santa Clara) surface-treated with an aminosilane-based coupling agent (KBM 573, manufactured by Santa Clara, inc.) was changed from 280 parts to 160 parts, and 96 parts of hollow silica (BA-S, average particle size 2.6 μm, void content 25 vol%) surface-treated with an aminosilane-based coupling agent (KBM 573, manufactured by Santa Clara, inc.) was further mixed.
(method for measuring average porosity of inorganic filler)
The density of the inorganic filler was measured using a true density measuring apparatus (ULTRAPYCOMETER 1000, manufactured by QUANTACHOME Co.). In this measurement, nitrogen gas was used as the measurement gas. Then, using the measured density (measured value) D M (g/cm 3 ) And a mass density (theoretical value) D of an inorganic material (silica) forming an inorganic filler T (g/cm 3 ) The average porosity of the inorganic filler was measured according to the above formula (I). In the above formula (I), the mass density (theoretical value) of silica as an inorganic material was set to 2.2g/cm 3 。
Comparative example 1 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 6 parts of a curing accelerator (MEK solution of 5 mass% of solid content) was used instead of 6 parts of a curing accelerator a (2, 4-diamino-6- [2- (2-undec-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine, 2-methoxypropanol solution of 5 mass% of solid content).
Comparative example 2 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 6 parts of a curing accelerator (2, 4-diamino-6- [2- (2-undecyl-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine, a 2-methoxypropanol solution having a solid content of 5 mass%) was used instead of 6 parts of the curing accelerator (2P 4MZ, 2-phenyl-4-methylimidazole, a 2-methoxypropanol solution having a solid content of 5 mass%) in the resin composition.
Comparative example 3 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 6 parts of a curing accelerator (6 parts of a 2-methoxypropanol solution having a solid content of 5% by mass) was used instead of 6 parts of a curing accelerator a (2, 4-diamino-6- [2- (2-undecyl-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine, and 6 parts of a curing accelerator (a solution of TBP-DA, tetrabutylphosphonium decanoate, MEK, manufactured by the chemical industry co., ltd. Of four countries) were used.
Comparative example 4 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 6 parts of a curing accelerator ("DMAP", 4-dimethylaminopyridine, MEK solution having a solid content of 5% by mass) was used instead of 6 parts of a curing accelerator A (2, 4-diamino-6- [2- (2-undecyl-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine, 2-methoxypropanol solution having a solid content of 5% by mass).
Comparative example 5 >
A varnish-like resin composition was prepared in the same manner as in example 1 except that 6 parts of a curing accelerator A (2, 4-diamino-6- [2- (2-undecyl-1H-imidazol-1-yl) ethyl ] -1,3, 5-triazine, a solution of 5% by mass of solid content in 2-methoxypropanol) was not used.
Comparative example 6 >
A varnish-like resin composition was prepared in the same manner as in example 2, except that 3 parts of a vinyl compound (A-DOG, dioxane glycol diacrylate, manufactured by Xinzhou chemical Co., ltd.) was not used.
Test example 1: measurement of glass transition temperature and coefficient of linear thermal expansion of cured product
As a support, a PET film (AL 5, manufactured by Lindeke Co., ltd., thickness: 38 μm) with an alkyd-based release layer was prepared. The varnish-like resin compositions prepared in examples and comparative examples were uniformly applied to the release layer of the support so that the thickness of the dried resin composition layer became 40. Mu.m, and dried at 80 to 120℃for 5 minutes (average 100 ℃) to prepare a resin sheet.
The resin sheet having a thickness of 40 μm of the prepared resin composition layer was heated at 200℃for 90 minutes, and after the resin composition layer was thermally cured, the support was peeled off to obtain a cured product for evaluation. The cured product for evaluation was cut into test pieces having a width of 5mm and a length of 15 mm. The test piece was subjected to thermomechanical analysis by a tensile load method using a thermomechanical analysis device (Thermo Plus TMA8310, manufactured by Rigaku corporation). Specifically, after the test piece was mounted on the thermal mechanical analyzer, the test piece was continuously measured 2 times under a measurement condition of a load of 1g and a temperature rise rate of 5 ℃/min. In 2 measurements, the glass transition temperature (. Degree. C.) and the linear thermal expansion coefficient (ppm/K) in the plane direction in the range from 25℃to 150℃were calculated.
Test example 2: determination of relative permittivity and dielectric loss tangent of cured product
The cured product for evaluation obtained in the same manner as in test example 1 was cut into test pieces having a width of 2mm and a length of 80 mm. For this test piece, the relative permittivity and dielectric loss tangent were measured by the cavity perturbation method under conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23℃using "HP8362B" manufactured by Agilent technologies. The measurement was performed on 2 test pieces, and an average value was calculated.
Test example 3: evaluation of crack resistance >
(1) Preparation of inner substrate
Copper-clad laminates (copper foil 18 μm thick, substrate 0.4mm thick, "R1515A" manufactured by Song corporation) were laminated on both sides with a glass cloth substrate epoxy resin on which an inner layer circuit was formed, and the copper surfaces were roughened by etching 1 μm with a microetching agent (CZ 8101 manufactured by Meger (MEC)) to obtain a roughened copper surface.
(2) Lamination of resin sheets
Resin sheets obtained in the same manner as in test example 1 were laminated on both sides of the inner substrate using a batch vacuum laminator ("CVP 700" from Nikko Materials, level 2 lamination laminator) so that the resin composition layer was in contact with the inner 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℃for 30 seconds under a pressure of 0.74 MPa. Next, hot pressing was performed at 100℃under a pressure of 0.5MPa for 60 seconds.
(3) Thermosetting of resin composition layer
The inner substrate laminated with the resin sheet was put into an oven at 130 ℃ and heated for 30 minutes, and then moved into an oven at 170 ℃ and heated for 30 minutes, so that the resin composition layer was thermally cured, thereby forming an insulating layer. Then, the support is peeled off to obtain a cured substrate having an insulating layer, an inner substrate, and an insulating layer in this order.
(4) Roughening treatment
For the cured substrate, a desmear treatment is performed as a roughening treatment. As the desmear treatment, the following wet desmear treatment was performed.
(Wet contamination removal treatment)
The cured substrate was immersed in a swelling solution (an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide, manufactured by Anmei Japan Co., ltd.) at 60℃for 5 minutes, followed by immersion in an oxidizing agent solution (an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80℃for 20 minutes. Next, the resultant was immersed in a neutralization solution (America Japanese company, "Reduction Solution Securiganth P", aqueous sulfuric acid solution) at 40℃for 5 minutes, and then dried at 80℃for 15 minutes.
According to JIS K5600-5-6, cut marks were introduced in a checkerboard network on the evaluation substrate after the roughening treatment by wet desmutting treatment, and the presence or absence of cracks of the cured coating film was observed and evaluated with an optical microscope. Specifically, cut marks were formed in a grid pattern at 1mm intervals on the cured coating film of the evaluation substrate, and 10 coating film pieces were formed in the longitudinal direction, 10 coating film pieces were formed in the transverse direction, and a total of 100 coating film pieces were formed. Here, the coating film pieces represent portions of the cured coating film divided by the cuts. The 100 pieces of coated film were observed with an optical microscope, and the number of cracked coated film pieces was counted. Based on the ratio of the number of cracked coated sheets to 100 total coated sheets, crack resistance was evaluated according to the following evaluation criteria.
Evaluation criterion
"good" is shown in the following description: almost no cracks (less than 5%) on the cured coating film
"DELTA": there were few cracks (5% or more and less than 15%) in the cured coating film
"×": the cured coating film had a large number of cracks (15% or more).
The content of the nonvolatile components contained in the resin compositions of each example and comparative example, and the measurement results and evaluation results of the test examples are summarized in table 1 below.
TABLE 1
Figure BDA0004027249520000411
From the results shown in table 1, it is apparent that a cured product excellent in crack resistance can be obtained by using a resin composition comprising (a) an epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a curing accelerator, wherein component (C) comprises (C1) a compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.
The present application is based on Japanese patent application No. 2022-001258 (App. 2022, 1, 6) filed by the Japanese patent office, the contents of which are incorporated herein in their entirety.

Claims (20)

1. A resin composition comprising (A) an epoxy resin, (B) a compound containing a radical polymerizable group, and (C) a curing accelerator,
wherein the component (C) comprises: (C1) A compound having a nitrogen-containing heterocycle substituted with a hydrocarbon group having 7 or more carbon atoms.
2. The resin composition according to claim 1, wherein,
(C1) The component (C) comprises a compound shown in a formula (C),
Figure FDA0004027249510000011
in the formula (C), the components of the compound,
R 1 an alkyl group having 7 or more carbon atoms or an alkenyl group having 7 or more carbon atoms;
R 2 represents a hydrogen atom, an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an aryl group optionally having a substituent, or a heteroaryl group optionally having a substituent;
R 3 and R is 4 Each independently represents a hydrogen atom or a substituent, or R 3 And R is 4 Bonded together to form an optionally substituted aromatic ring or an optionally substituted non-aromatic ring;
the double line consisting of a dotted line and a solid line represents a single bond or a double bond.
3. The resin composition according to claim 2, wherein,
R 2 is a group represented by the formula (R2),
Figure FDA0004027249510000012
in the formula (R2), the amino acid sequence of the formula (I),
x represents an alkylene group having 1 to 6 carbon atoms;
y represents a single bond, -O-, -CO-, -S-, -SO 2 -, -NH-, -COO-; -OCO- -CONH-or-NHCO-; * Indicating the bonding site.
4. The resin composition according to claim 1, wherein the content of the component (C1) is 0.001 to 1% by mass based on 100% by mass of the nonvolatile component in the resin composition.
5. The resin composition according to claim 1, wherein the content of the component (A) is 10 to 30% by mass based on 100% by mass of the nonvolatile component in the resin composition.
6. The resin composition according to claim 1, further comprising (D) an inorganic filler.
7. The resin composition according to claim 6, wherein the material of component (D) comprises a material selected from the group consisting of silica, alumina, and aluminosilicate.
8. The resin composition according to claim 6, wherein the content of the component (D) is 70% by mass or more based on 100% by mass of the nonvolatile component in the resin composition.
9. The resin composition according to claim 1, further comprising (E) an epoxy resin curing agent.
10. The resin composition according to claim 9, wherein component (E) comprises an active ester-based curing agent.
11. The resin composition according to claim 9, wherein component (E) comprises a phenolic curing agent.
12. The resin composition according to claim 1, wherein a cured product of the resin composition has a relative dielectric constant (Dk) of 3.5 or less when measured at 5.8GHz and 23 ℃.
13. The resin composition according to claim 1, wherein a dielectric loss tangent (Df) of a cured product of the resin composition is 0.005 or less when measured at 5.8GHz and 23 ℃.
14. The resin composition according to claim 1, wherein a coefficient of linear thermal expansion (CTE) of a cured product of the resin composition is 25ppm/K or less in a range of 25℃to 150 ℃.
15. The resin composition according to claim 1, wherein a cured product of the resin composition has a glass transition temperature (Tg) of 150℃or higher.
16. A cured product of the resin composition according to any one of claims 1 to 15.
17. A sheet laminate comprising the resin composition according to any one of claims 1 to 15.
18. A resin sheet, comprising:
support body
A resin composition layer formed of the resin composition according to any one of claims 1 to 15, provided on the support.
19. A printed wiring board, wherein an insulating layer is provided,
the insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 15.
20. A semiconductor device comprising the printed wiring board according to claim 19.
CN202211710590.8A 2022-01-06 2022-12-29 Resin composition Pending CN116396444A (en)

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