CN117887207A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN117887207A
CN117887207A CN202311305747.3A CN202311305747A CN117887207A CN 117887207 A CN117887207 A CN 117887207A CN 202311305747 A CN202311305747 A CN 202311305747A CN 117887207 A CN117887207 A CN 117887207A
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China
Prior art keywords
resin composition
mass
resin
epoxy resin
less
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CN202311305747.3A
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Chinese (zh)
Inventor
川合贤司
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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Publication of CN117887207A publication Critical patent/CN117887207A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

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

Abstract

The invention provides a resin composition which can obtain a cured product having excellent crack resistance after a stain removal treatment while suppressing the dielectric loss tangent to be lower even in a high-temperature environment. The solution of the present invention is a resin composition comprising (A) an organic filler having liquid crystallinity, (B) an epoxy resin, and (C) an active ester compound.

Description

Resin composition
Technical Field
The present invention relates to a resin composition comprising an epoxy resin. The present invention also relates to a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device each obtained from 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 the manufacturing method using the stacked method, the insulating layer is generally formed by curing a resin composition. As an insulating layer of a printed wiring board of a semiconductor device, it is required to exhibit good dielectric characteristics (low dielectric constant, low dielectric loss tangent) in order to suppress transmission loss during operation in a high-frequency environment.
As a resin composition that gives a cured product exhibiting good dielectric characteristics, for example, a resin composition containing an active ester compound as a curing agent for an epoxy resin is reported in patent document 1.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2009-235165.
Disclosure of Invention
Technical problem to be solved by the invention
The resin composition containing the active ester compound as a curing agent as described in patent document 1 gives a cured product having excellent dielectric characteristics as compared with the case of using a general phenol curing agent, but tends to be cracked after the stain removal treatment. Further, it has been found that a semiconductor device is sometimes exposed to a high-temperature environment when operated in a high-frequency environment or the like, but even a material exhibiting good dielectric characteristics in a room-temperature environment may be deteriorated in dielectric characteristics (particularly dielectric loss tangent) in a high-temperature environment, and desired dielectric characteristics may not be achieved in an environment where it is actually used.
The subject of the invention is to provide: a resin composition which can be used for a cured product having low dielectric loss tangent even in a high-temperature environment and excellent crack resistance after a stain-removing treatment, and a cured product, a sheet-like laminate, a resin sheet, a printed wiring board, and a semiconductor device obtained by using the resin composition can be obtained.
Technical proposal adopted for solving the technical problems
As a result of intensive studies to solve the problems of the present invention, the present inventors have found that, by using an epoxy resin and an active ester compound as components of a resin composition and further containing an organic filler having liquid crystallinity, a cured product can be obtained which can suppress occurrence of cracks after a desmear treatment while suppressing the dielectric loss tangent even in a high-temperature environment to be low, and have completed the present invention.
Namely, the present invention includes the following:
[1] a resin composition comprising (A) an organic filler having liquid crystallinity, (B) an epoxy resin, and (C) an active ester compound;
[2] the resin composition according to the above [1], wherein the content of the component (A) is 0.1% by mass or more and 10% by mass or less, based on 100% by mass of the resin component in the resin composition;
[3] the resin composition according to the above [1] or [2], wherein (A) the melting point of the organic filler having liquid crystallinity is 270 ℃ or higher;
[4] the resin composition according to any one of the above [1] to [3], wherein (D) an inorganic filler is further contained;
[5] The resin composition according to any one of the above [1] to [4], further comprising (E) a radical polymerizable compound;
[6] the resin composition according to any one of the above [1] to [5], which is used for forming an interlayer insulating layer of a printed wiring board;
[7] a cured product of the resin composition layer according to any one of [1] to [6] above;
[8] a sheet laminate comprising the resin composition according to any one of the above [1] to [6 ];
[9] 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 [6] provided on the support;
[10] a printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of the above [1] to [6 ];
[11] a semiconductor device comprising the printed wiring board according to [10] above.
ADVANTAGEOUS EFFECTS OF INVENTION
If the invention is adopted, the following steps can be provided: a resin composition which can provide a cured product having excellent crack resistance after a stain-removing treatment while keeping the dielectric loss tangent low even in a high-temperature environment, a cured product of the resin composition, a sheet-like laminate and a resin sheet each comprising the resin composition, and a printed wiring board and a semiconductor device each comprising the cured product of the resin composition.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples described below, and may be implemented by arbitrarily changing the embodiments and examples within the scope of the claims and the equivalents thereof.
In the following description, unless otherwise indicated, the amounts of the respective components are the amounts of nonvolatile components. In the following description, unless otherwise indicated, "nonvolatile components in the resin composition" means that the inorganic filler (D) may be included, but unless otherwise indicated, "resin components" means components other than the inorganic filler (D) among the nonvolatile components contained in the resin composition.
< resin composition >
The resin composition of the present invention comprises (A) an organic filler having liquid crystallinity, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product having excellent crack resistance after the stain removal treatment can be obtained while suppressing the dielectric loss tangent to a low level even in a high-temperature environment such as 90 ℃. In the present invention, a cured product having a low dielectric loss tangent at room temperature or a room temperature range such as 23℃can be obtained.
The resin composition of the present invention may further contain any component in addition to (a) the organic filler having liquid crystallinity, (B) the epoxy resin, and (C) the active ester compound. Examples of the optional components include (D) an inorganic filler, (E) a radical polymerizable compound, (F) another curing agent, (G) a curing accelerator, (H) another additive, and (K) an organic solvent. In the present specification, the components (a) to (K) are sometimes referred to as "(a) component", "(B) component", and the like, respectively. The components contained in the resin composition will be described in detail below.
(A) organic filler having liquid crystallinity
(A) The organic filler having liquid crystallinity is specifically a filler containing an organic polymer having liquid crystallinity, and may be a filler formed of an organic polymer having liquid crystallinity. (A) The components may be used alone or in combination of at least 2. In the present specification, "having liquid crystallinity" means that anisotropy is observed in a polarization microscope when heated to a temperature not lower than the melting point.
Examples of the organic polymer having liquid crystallinity include general liquid crystal polymers, for example, wholly aromatic polyesters (poly-wholly aromatic esters) synthesized from p-hydroxybenzoic acid, biphenol, terephthalic acid and the like, and specifically, those having a structural unit ([ -O-C) derived from p-hydroxybenzoic acid 6 H 4 -CO-]) Structural units derived from diphenols ([ -O-C) 6 H 4 -C 6 H 4 -O-]) Structural units derived from terephthalic acid ([ -OC-C) 6 H 4 -CO-]) At least 1 structural unit of the polymer. The structural unit referred to in the present specification includes a repeating unit present in the main chain of the polymer and a unit or a terminal group present at a terminal or side chain. As the liquid crystal polymer, for example, liquid crystal polymer particles described in Japanese patent application laid-open No. 2022-79336 can be preferably used.
The melting point of the organic polymer having liquid crystallinity is preferably 270℃or higher, more preferably 280℃or higher, further preferably 290℃or higher, and as an upper limit, preferably 370℃or lower, more preferably 360℃or lower, further preferably 350℃or lower. In the present specification, the melting point of the liquid crystal polymer is measured by a Differential Scanning Calorimeter (DSC) manufactured by Hitachi High-Tech Science Co., ltd, according to the test method of ISO11357 and ASTM D3418.
When the organic polymer having liquid crystallinity has the above-mentioned melting point, the resin composition of the present invention is not easily compatible with (B) an epoxy resin having a generally small average molecular weight and (C) an active ester compound even under a general curing condition, and is advantageous in that stress relaxation of a cured product obtained by using the resin composition tends to improve crack resistance after a stain removal treatment.
The filler as component (A) is preferably particles, powder or powder, and the particle size distribution of the powder is, for example, D50 (median particle diameter) representing 50% of the particle diameter accumulated from the side where the particle diameter is small is, for example, 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.4 μm or more, still more preferably 0.5 μm or more, still more preferably 1 μm or more, particularly preferably 3 μm or more, for example, 12 μm or less, 10 μm or less, preferably 8 μm or less, more preferably 6 μm or less, still more preferably 5.5 μm or less, particularly preferably 5 μm or less. The particle size can be measured by a laser diffraction scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be 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.
The amount of acetic acid of the release gas (out gas) generated after the organic polymer having liquid crystallinity is subjected to the heat treatment at 190℃for 1 hour is, for example, 10ppm or less, preferably 5ppm or less, more preferably 1ppm or less. The amount of acetic acid which is a gas released from the organic polymer having liquid crystallinity can be controlled by adjusting the conditions in the synthesis step of the liquid crystal polymer as a raw material, for example, the heating temperature and time of the solid phase polymerization. If the amount of acetic acid released from the gas is small as described above, the increase in dielectric loss tangent of the cured product obtained by using the resin composition is easily reduced even in a state where the molecular motion is generally increased under a high-temperature environment.
The dielectric loss tangent (measurement frequency: 10 GHz) of the organic polymer having liquid crystallinity is 0.001 or less, preferably 0.0009 or less, more preferably 0.0008 or less, and even more preferably 0.0007 or less. This value is a measured value of dielectric loss tangent in the in-plane direction of an injection molded article of an organic polymer having liquid crystallinity. The injection-molded article was a plate-like test piece of 30mm×30mm×0.4mm (thickness).
The mechanism of the resin composition of the present invention is not necessarily clear, but it is presumed that the inclusion of the component (a) having liquid crystallinity, i.e., having a rigid portion in the molecule, can reduce the increase in dielectric loss tangent even in a state where the molecular motion is generally intensified in a high-temperature environment in a cured product obtained by using the resin composition, and the component (a) does not react with the active ester compound (C), so that stress relaxation in the cured product is facilitated, and crack resistance after stain removal treatment can be improved. (A) The component (c) is preferably an epoxy resin, more preferably a resin which is insoluble in the resin composition even if the resin composition of the present invention contains a resin other than the component (c), even more preferably a resin which is insoluble in the resin composition even if the resin composition of the present invention contains an organic solvent.
The content of the component (a) is, for example, 0.1 mass% or more, preferably 0.3 mass% or more, more preferably 0.4 mass% or more, still more preferably 0.5 mass% or more, still more preferably 0.55 mass% or more, and is, for example, 5 mass% or less, preferably 4 mass% or less, more preferably 3.5 mass% or less, still more preferably 3 mass% or less, and still more preferably 2.5 mass% or less, relative to 100 mass% of the nonvolatile component in the resin composition.
The content of the component (a) is, for example, 0.1 mass% or more, preferably 0.5 mass% or more, more preferably 1 mass% or more, still more preferably 1.5 mass% or more, still more preferably 2 mass% or more, and is, for example, 12 mass% or less, preferably 10 mass% or less, more preferably 9.5 mass% or less, still more preferably 9 mass% or less, still more preferably 8.5 mass% or less, relative to 100 mass% of the resin component in the resin composition.
Epoxy resin (B)
The resin composition of the present invention contains (B) an epoxy resin. (B) The epoxy resin is a curable resin having an epoxy group.
Examples of the epoxy resin (B) include: a bisxylenol (bispyrinol) 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 (naphthol novolac) type epoxy resin, a phenol novolac (phenol novolac) type epoxy resin, a tert-butylcatechol type epoxy resin, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a glycidolamine type epoxy resin, a glycidol 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 cycloaliphatic epoxy resin, a heterocyclic type epoxy resin, a spiro ring-containing epoxy resin, a cyclohexane type epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthalene ether type epoxy resin, a trimethylol type epoxy resin, a tetraphenylethane type epoxy resin, an isocyanurate type epoxy resin, a phthalone (phenol phthalimidine) type epoxy resin, a phthalone (phenol phthalone) or the like. (B) The epoxy resin may be used alone or in combination of 1 kind or 2 or more kinds.
The resin composition preferably contains, as the (B) epoxy resin, 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, based on 100% by mass of the nonvolatile component of the (B) epoxy resin.
Examples of the epoxy resin include an epoxy resin which is liquid at a temperature of 20 ℃ (hereinafter also referred to as "liquid epoxy resin") and an epoxy resin which is solid at a temperature of 20 ℃ (hereinafter also referred to as "solid epoxy resin"). The resin composition of the present invention may contain only a liquid epoxy resin as an epoxy resin, or may contain only a solid epoxy resin, or may contain a liquid epoxy resin and a solid epoxy resin in combination. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, more preferably 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, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, and epoxy resin having a butadiene structure are preferable.
Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC, and "828US", "828EL", "jER828EL", "825", "EPIKOTE 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi chemical Co., ltd, and "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi chemical Co., ltd, and "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi chemical Co., ltd, and "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi chemical Co., ltd, and "ED-523T" (Glycirol type epoxy resin) manufactured by ADEKA Co., ltd, EP-3950L (manufactured by ADEKA) and EP-3980S (glycidylamine type epoxy resin), EP-4088S (manufactured by ADEKA) and ZX1059 (manufactured by Nippon Kagaku Co., ltd.) (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), EX-721 (glycidylester type epoxy resin) manufactured by Nagase Chemtex Co., ltd.), "CELLOXIDE 2021P" (alicyclic epoxy resin having an ester skeleton) made by Dairy Celloxide, PB-3600 made by Dairy Celloxide, JP-100"," JP-200 "made by Japanese Sedan, inc. (epoxy resin having butadiene structure), ZX1658 made by Nikko Kagaku, new Japanese Kogyo Co., ltd.), "ZX1658GS" (liquid 1, 4-glycidyl cyclohexane type epoxy resin) and the like. These resins may be used alone or in combination of 1 or more than 2.
The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, 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 naphthalene-ether-type epoxy resin, an anthracene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol AF-type epoxy resin, a phenol aralkyl-type epoxy resin, a tetraphenyl ethane-type epoxy resin, a phenol benzopyrrolone-type epoxy resin, a phenolphthalein-type epoxy resin.
Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Co., ltd., "HP-4700" manufactured by DIC Co., ltd., and "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" (cresol novolak type epoxy resin) manufactured by DIC Co., ltd., and "N-695" (cresol novolak type epoxy resin) manufactured by DIC Co., ltd., and "HP-7200" manufactured by DIC Co., ltd., and "HP-7200H" and "HP-7200L" (dicyclopentadiene type epoxy resin), and "EXA-7311" manufactured by DIC Co., ltd., and "EXA-7311-G3", "EXA-7311-G4S" and "HP6000" (naphthalene type epoxy resin), and "EPPN-H" (triphenol type epoxy resin) manufactured by Japanese chemical Co., ltd.), "NC7000L" (naphthol novolac type epoxy resin) made by Kagaku Kogyo Co., ltd., NC3000H "," NC3000L "," NC3000FH "," NC3100 "(biphenyl type epoxy resin) made by Kagaku Kogyo Co., ltd., ESN475V" (naphthalene type epoxy resin) made by Migaku Kogyo Co., ltd., ESN485 "(naphthol type epoxy resin) made by Migaku Kogyo Co., ltd., ESN375" (dihydroxynaphthalene type epoxy resin) made by Migaku Kogyo Co., YX4000H "," YX4000HK "" YL7890 "(dimethl type epoxy resin) made by Migaku Kogyo Co., ltd., YL6121" (biphenyl type epoxy resin) made by Migaku Kogyo Co., ltd., "YX8800" manufactured by mitsubishi chemical corporation (anthracene-type epoxy resin), "YX7700" manufactured by mitsubishi chemical corporation (phenol aralkyl-type epoxy resin), "PG-100" manufactured by osaka gas chemical corporation (CG-500), "YL7760" manufactured by mitsubishi chemical corporation (bisphenol AF-type epoxy resin), "YL7800" manufactured by mitsubishi chemical corporation (fluorene-type epoxy resin), "jER1010" manufactured by mitsubishi chemical corporation (bisphenol a-type epoxy resin), "jER1031S" manufactured by mitsubishi chemical corporation (tetraphenyl ethane-type epoxy resin), and "WHR991S" manufactured by japan chemical corporation (phenol benzopyrrolidone-type epoxy resin). These resins may be used alone or in combination of 1 or more than 2.
In the case where the liquid epoxy resin and the solid epoxy resin are used in combination, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin/solid epoxy resin) is not particularly limited, but is preferably 10 or less, more preferably 5 or less, and further more preferably 1 or less.
(B) 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 corresponding to each 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.
(B) 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 in terms of polystyrene by Gel Permeation Chromatography (GPC).
The content of the component (B) is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, still more preferably 8.5% by mass or more, and is, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 13% by mass or less, still more preferably 10% by mass, relative to 100% by mass of the nonvolatile component in the resin composition.
The content of the component (B) is, for example, 10 mass% or more, preferably 15 mass% or more, more preferably 20 mass% or more, still more preferably 25 mass% or more, still more preferably 28 mass% or more, particularly preferably 30 mass% or more, and is, for example, 60 mass% or less, preferably 55 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% or less, still more preferably 40 mass% or less, particularly preferably 35 mass% or less, relative to 100 mass% of the resin component in the resin composition.
Active ester compound (C)
The resin composition of the present invention contains (C) an active ester compound. (C) The active ester compound may be used alone in 1 kind, or may be used in combination of 2 or more kinds in any ratio. (C) The active ester compound may have a function of reacting with (B) the epoxy resin to crosslink the (B) the epoxy resin. The active ester compound (C) may be a compound having a carbon-carbon unsaturated bond, and the unsaturated bond is preferably a carbon-carbon double bond, and may be, for example, a bond similar to the carbon-carbon unsaturated bond of the component (C1) described later.
As the active ester compound (C), a compound 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, is 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 (Phenolic Novolac). The "dicyclopentadiene type phenol compound" refers to a phenol compound obtained by condensing 2 molecules of phenol with 1 molecule of dicyclopentadiene.
Specifically, as the (C) active ester compound, a dicyclopentadiene type active ester compound, a naphthalene type active ester compound containing a naphthalene structure, an active ester compound containing an acetyl compound of a novolac resin, an active ester compound containing a benzoyl compound of a novolac resin are preferable, and among these, at least 1 selected from the dicyclopentadiene type active ester compound and naphthalene type active ester compound is more preferable, and a dicyclopentadiene type active ester compound is still more preferable. As the dicyclopentadiene type active ester compound, an active ester compound containing a dicyclopentadiene type diphenol structure is preferable. "dicyclopentadiene type diphenol structure" means a 2-valent structural unit formed from phenylene-dicyclopentylene-phenylene.
As the commercial product of the active ester compound (C), examples of the active ester compound containing a dicyclopentadiene type diphenol structure include "EXB9451", "EXB9460S", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000-65T", "HPC-8000H-65TM" (manufactured by DIC Co., ltd.); examples of the naphthalene structure-containing active ester compound include "EXB-8100L-65T", "EXB-8150-60T", "EXB-8150-62T", "EXB-9416-70BK", "HPC-8150-60T", "HPC-8150-62T" (manufactured by DIC Co., ltd.); examples of the phosphorus-containing active ester compound include "EXB9401" (available from DIC Co., ltd.); examples of the active ester compound which is an acetylated compound of a novolac resin include "DC808" (manufactured by mitsubishi chemical corporation); examples of the active ester compound which is a benzoyl compound of the novolac resin include "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi chemical corporation); examples of the active ester compound containing a styryl group and a naphthalene structure include "PC1300-02-65MA" (manufactured by Aiwalter Co., ltd.).
(C) The active ester group equivalent of the active ester compound is preferably 50g/eq to 500g/eq, more preferably 50g/eq to 400g/eq, still more preferably 100g/eq to 300g/eq. The active ester group equivalent is the mass of the active ester compound corresponding to 1 equivalent of active ester group.
When the total sum of the mass of the nonvolatile component of the component (B) divided by the epoxy equivalent weight is a and the total sum of the mass of the nonvolatile component of the component (C) divided by the active ester equivalent weight is B, the ratio of B/a is preferably 1.0 or more, more preferably 1.01 or more, still more preferably 1.03 or more, still more preferably 1.05 or more, particularly preferably 1.1 or more, yet more preferably 2.0 or less, still more preferably 1.75 or less, still more preferably 1.5 or less, still more preferably 1.3 or less, and particularly preferably 1.2 or less. The effect of the present invention can be easily obtained by making the amount ratio of the (B) component to the (C) component within the above-mentioned range.
The content of the component (C) is, for example, 3 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, still more preferably 13 mass% or more, still more preferably 15 mass% or more, and is, for example, 30 mass% or less, preferably 25 mass% or less, more preferably 20 mass% or less, still more preferably 16 mass% or less, relative to 100 mass% of the nonvolatile component in the resin composition.
The content of the component (C) is, for example, 30 mass% or more, preferably 40 mass% or more, more preferably 45 mass% or more, still more preferably 50 mass% or more, still more preferably 54 mass% or more, and is, for example, 70 mass% or less, preferably 65 mass% or less, more preferably 63 mass% or less, still more preferably 60 mass% or less, relative to 100 mass% of the resin 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. (D) The inorganic filler may be used alone or in combination of at least 2 kinds.
As the material of the inorganic filler (D), an inorganic compound is used. Examples of the material of the inorganic filler (D) include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate. Among them, silica is particularly preferable. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Further, as the silica, spherical silica is preferable. (D) The inorganic filler may be used alone in 1 kind, or may be used in combination of 2 or more kinds in any ratio.
Examples of the commercial products of the inorganic filler (D) include "SP60-05", "SP507-05", manufactured by Nikka chemical Co., ltd., "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", "YC100C", "YA050C-MJE", "YA010C", manufactured by DENKA Co., ltd., "UFP-30", "DAW-03", "FB-105FD", manufactured by Tokuyama Co., ltd., "SILFIL NSS-3N", "SILFIL NSS-4N", "SILFIL NSS-5N", manufactured by Tokuyama Co., ltd., "MGH-005", manufactured by Takara Shuzo Co., ltd., and "BA-S" manufactured by Nippon cement Co., ltd., and the like.
(D) The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 2 μm or less, still more preferably 1 μm or less, particularly preferably 0.7 μm or less. (D) The lower limit of the average particle diameter of the 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. (D) 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, blue and red were used as light source wavelengths, a volume-based particle size distribution of an inorganic filler was measured by a flow cell (flow cell), and an average particle size was calculated from the obtained particle size distribution as a median particle size. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, inc.
(D) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1m 2 Preferably at least 0.5m 2 Preferably at least/g, more preferably at least 1m 2 Preferably at least 3m 2 And/g. (D) The upper limit of the specific surface area of the 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 by a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.
(D) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the inorganic filler (D) can be improved. Examples of the surface treatment agent include: vinyl silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane, acryl silane coupling agents such as 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, epoxy silane coupling agents such as 3-epoxypropoxypropyltriethoxysilane, styryl silane coupling agents such as p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, acryl silane coupling agents such as 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane-N- (1, 3-dimethylpropylenepropylamine-N-phenyl-trioxypropyl silane, N-8-aminophenylpropyltrimethoxysilane, amino silane coupling agents such as N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl trimethoxysilane, isocyanurate silane coupling agents such as tris (trimethoxysilylpropyl) isocyanurate, ureido silane coupling agents such as 3-ureido propyl trialkoxysilane, mercapto silane coupling agents such as 3-mercaptopropyl methyl dimethoxy silane and 3-mercaptopropyl trimethoxy silane, isocyanate silane coupling agents such as 3-isocyanatopropyl triethoxy silane, and silane coupling agents such as anhydride silane coupling agents such as 3-trimethoxysilylpropyl succinic anhydride; non-silane coupling-alkoxysilane compounds such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilyl) hexane, and trifluoropropyltrimethoxysilane. The surface treatment agent may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds.
Examples of the commercial product of the surface treatment agent include: "KBM-1003", "KBE-1003" (vinyl silane coupling agent), "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent), "KBM-1403" (styrene silane coupling agent), "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacryl silane coupling agent), "KBM-5103" (acryl silane coupling agent), "KBM-602", "KBM-603", "KBM-903", "KBE-9103P", "KBM-573", "KBM-575" (amino silane coupling agent), "KBM-9659" (isocyanurate type silane coupling agent), "KBE-585" (ureido type silane coupling agent), "KBM-802", "KBM-803" (mercapto type silane coupling agent), "KBE-9007N" (isocyanate type silane coupling agent), "X-12-967C" (anhydride type silane coupling agent), "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3083", "KBM-3103C", "KBM-3066", and the like, "KBM-7103" (non-silane-coupled-alkoxysilane compound) and the like.
The degree of surface treatment with the surface treatment agent is preferably within a predetermined range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, the inorganic filler is preferably surface-treated with 0.2 to 5 mass% of a surface-treating agent, more preferably 0.2 to 3 mass% of a surface-treating agent, and even more preferably 0.3 to 2 mass% of a surface-treating agent.
The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The carbon amount per unit surface area of the inorganic filler is preferably 0.02mg/m from the viewpoint of improving the dispersibility of the inorganic filler 2 The above is more preferably 0.1mg/m 2 The above is more preferably 0.2mg/m 2 The above. On the other hand, from the melt viscosity of the resin composition and preventing the rise of the melt viscosity in the form of a sheetFrom the viewpoint, it is preferably 1.0mg/m 2 Hereinafter, more preferably 0.8mg/m 2 The following is more preferable to be 0.5mg/m 2 The following is given.
(D) The carbon amount per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is subjected to a washing treatment with a solvent such as Methyl Ethyl Ketone (MEK). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with the surface treating agent, and the mixture was ultrasonically cleaned at 25 ℃ for 5 minutes. After the supernatant is removed and the solid component is dried, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, EMIA-320V manufactured by horiba, inc. can be used.
The content of the inorganic filler (D) in the resin composition is not particularly limited, but is preferably 95 mass% or less, more preferably 90 mass% or less, still more preferably 85 mass% or less, still more preferably 80 mass% or less, particularly preferably 75 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the inorganic filler (D) in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100% by mass, it may be, for example, 0% by mass or more, 1% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, etc., 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.
(E) radical polymerizable Compound
The resin composition of the present invention may contain (E) a radical polymerizable compound as an optional component. (E) The radical polymerizable compound may be used alone or in combination of 2 or more kinds.
The radical polymerizable compound is not particularly limited as long as it has 1 or more, preferably 2 or more radical polymerizable unsaturated groups in 1 molecule. Examples of the radical polymerizable compound include compounds having 1 or more groups selected from maleimide groups, vinyl groups, allyl groups, styryl groups, vinylphenyl groups, acryl groups, methacryl groups, fumaryl groups, and maleimide groups as radical polymerizable unsaturated groups. Among them, from the viewpoint of easy obtaining of a cured product excellent in dielectric characteristics, it is preferable to contain (E1) a maleimide compound and/or (E2) another radical polymerizable compound. (E2) The other radical polymerizable compound is a compound having not a maleimide group but a radical polymerizable unsaturated group other than a maleimide group, and among these, it is preferable to contain 1 or more kinds selected from (meth) acrylic resins and styrene-based resins.
The type of the maleimide compound (E1) is not particularly limited as long as it has 1 or more, preferably 2 or more maleimide groups (2, 5-dihydro-2, 5-dioxo-1H-pyrrol-1-yl) in 1 molecule. Examples of the maleimide compound include: "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by design molecule (Designer Molecules)) and the like, which contain a maleimide resin derived from an aliphatic skeleton having 36 carbon atoms of dimer diamine; maleimide resins containing an indane skeleton described in Japanese patent application laid-open No. 2020-500211; and maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of a maleimide group such as MIR-3000-70MT, MIR-5000-60T (all made by Kagaku Kogyo Co., ltd.), BMI-4000 (made by Daiko Kagaku Kogyo Co., ltd.), BMI-80 (made by KI Kagaku Kogyo Co., ltd.).
The type of the (meth) acrylic resin is not particularly limited as long as it has 1 or more, preferably 2 or more (meth) acryloyl groups in 1 molecule. Herein, the term "(meth) acryl" refers to the generic term for acryl and methacryl. Examples of THE methacrylic resin include (meth) acrylic resins such as "A-DOG" (manufactured by Xinzhou chemical Co., ltd.), "DCP-A" (manufactured by Kagaku chemical Co., ltd.), "NPDGA", "FM-400", "R-687", "THE-330", "PET-30", "DPHA" (manufactured by Nippon Kagaku Co., ltd.).
The kind of the styrene-based resin is not particularly limited as long as it has 1 or more, preferably 2 or more styrene groups or vinylphenyl groups in 1 molecule. Examples of the styrene-based resin include "OPE-2St", "OPE-2St1200" and "OPE-2St 2200" (all made by Mitsubishi gas chemical Co., ltd.).
The content of the radical polymerizable compound (E) in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, particularly preferably 1.5% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.
The content of the radical polymerizable compound (E) in the resin composition may be 0% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, particularly preferably 2.5% by mass or more, and for example, 20% by mass or less, preferably 10% by mass or less, more preferably 7% by mass or less, particularly preferably 5% by mass or less, based on 100% by mass of the resin component in the resin composition.
(F) other curing Agents
The resin composition of the present invention may contain (F) other curing agent as an optional component. The other curing agent (F) does not include any of the above components (A) to (C) and (E). (F) The other curing agent may have a function as an epoxy resin curing agent for curing the resin composition by reacting with the epoxy resin (B) as in the case of the above-mentioned (C) active ester compound. (F) The other curing agents may be used alone or in combination of 1 or more than 2.
Examples of the other curing agent (F) include phenol curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate curing agents, and thiol curing agents. Among them, it is preferable to use 1 or more curing agents selected from the group consisting of phenolic curing agents and carbodiimide curing agents.
As the phenolic curing agent, a curing agent having 1 or more, preferably 2 or more hydroxyl groups bonded to an aromatic ring such as a benzene ring or naphthalene ring in 1 molecule can be used. From the viewpoints of heat resistance and water resistance, a phenolic curing agent having a phenolic structure is preferable. Further, from the viewpoint of adhesion, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable. Among them, a novolak resin having a triazine skeleton is preferable from the viewpoint of highly satisfying heat resistance, water resistance and adhesion. Specific examples of the phenolic curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Ming He Chemicals, japan chemical Co., ltd., "NHN", "CBN", "GPH", and "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395" manufactured by DIC, and "LA-7052", "LA-3018-50P", "LA-1356", "TD2090", "TD-2090-60M" manufactured by Nissan chemical Co., ltd.
As the carbodiimide-based curing agent, a curing agent having 1 or more, preferably 2 or more carbodiimide structures in 1 molecule can be used. Specific examples of the carbodiimide-based curing agent include: aliphatic dicarboximides such as tetramethylene-bis (t-butylcarbodiimide), and cyclohexanedis (methylene-t-butylcarbodiimide); aromatic dicarboximides such as phenylene-bis (xylyl carbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexyl carbodiimide) and poly (isophorone carbodiimide); and aromatic polycarbodiimides such as poly (phenylene carbodiimides), poly (naphthylene carbodiimides), poly (tolylene carbodiimides), poly (methyldiisopropylphenylene carbodiimides), poly (triethylphenylene carbodiimides), poly (diethylphenylene carbodiimides), poly (triisopropylphenylene carbodiimides), poly (diisopropylphenylene carbodiimides), poly (xylylene carbodiimides), poly (tetramethylxylylene carbodiimides), poly (methylenediphenylene carbodiimides), poly [ methylenebis (methylphenyl) carbodiimides ]. Examples of the commercially available carbodiimide curing agents include "CARBODILITE V-02B", "CARBODILITE V-03", "CARBODILITE V-04K", "CARBODILITE V-07" and "CARBODILITE V-09" manufactured by Nigrossedente chemical Co., ltd., "Stabaxol P", "Stabaxol P400" and "Hycasyl 510".
As the acid anhydride-based curing agent, a curing agent having 1 or more acid anhydride groups in 1 molecule, preferably a curing agent having 2 or more acid anhydride groups in 1 molecule, can be used. Specific examples of the acid anhydride-based curing agent include, for example: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2, 5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3'-4,4' -diphenyl sulfone tetracarboxylic dianhydride, 1, 3a,4,5,9 b-hexahydro-5- (tetrahydro-2, 5-dioxo-3-furanyl) -naphtho [1,2-C ] furan-1, 3-dione, ethylene glycol bis (dehydrated trimellitate), styrene-maleic anhydride copolymerized from styrene and maleic acid, and the like. Examples of the commercial products of the acid anhydride-based curing agent include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", made by Nippon chemical Co., ltd., and "YH306", "YH307", made by Mitsubishi chemical Co., ltd., HN-2200"," HN-5500", made by Hitachi chemical Co., ltd., and" EF-30"," EF-40"," EF-60"," EF-80", made by g Lei Weili, etc.
As the amine curing agent, a curing agent having 1 or more, preferably 2 or more amino groups in 1 molecule can be used. Examples of the amine curing agent include aliphatic amines, polyether amines, alicyclic amines, and aromatic amines, and among these, aromatic amines are preferable. The amine curing agent is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of the amine curing agent include: 4,4' -methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4' -diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine 4,4' -diaminodiphenyl ether, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane 3, 3-dimethyl-5, 5-diethyl-4, 4-diphenyl methane diamine, 2-bis (4-aminophenoxy) phenyl) propane, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, and the like. Examples of the commercial products of the amine curing agent include "SEIKACURE-S" manufactured by SEIKA, japan chemical Co., ltd., "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S", and "EPICURE W" manufactured by Mitsubishi chemical Co., ltd., "DTDA" manufactured by Sumitomo chemical Co., ltd.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP100D" made by JFE chemical Co., ltd. "ODA-BOZ", made by Showa Polymer Co., ltd. "HFB2006M" and "P-D" made by four-country chemical industry Co., ltd. "F-a".
Examples of the cyanate-based curing agent include: bisphenol a dicyanate, bisphenol cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenyl cyanate), 4' -ethylidene diphenyl dicyanate, hexafluorobisphenol a dicyanate, 2-bis (4-cyanooxy) phenylpropane, 1-bis (4-cyanooxyphenyl methane), bis (4-cyanooxy-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanooxyphenyl-1- (methylethylidene)) benzene, bis (4-cyanooxyphenyl) sulfide, bis (4-cyanooxyphenyl) ether, and polyfunctional cyanate resins derived from phenol novolac resins, cresol novolac resins, and the like, prepolymers obtained by triazinizing a part of these cyanate resins, and the like. Specific examples of the cyanate ester curing agent include "PT30" and "PT60" manufactured by Lonza Japan corporation (both of which are phenol novolac type multifunctional cyanate ester resins), "BA230" and "BA230S75" (prepolymers obtained by triazining part or all of bisphenol a dicyanate to form a trimer).
Examples of the thiol curing agent include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and tris (3-mercaptopropyl) isocyanurate.
(F) The reactive group equivalent of the other 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. Reactive group equivalent means the mass of the curing agent per 1 equivalent of reactive group.
The ratio of the amount of the epoxy resin to the amount of the curing agent, that is, the ratio of the amount of the component (B) to the amount of the component (C) and the amount of the component (F) to the amount of the reactive group equivalent are preferably 1.0 or more, more preferably 1.01 or more, still more preferably 1.1 or 1.10 or more, still more preferably 1.15 or more, particularly preferably 1.2 or more, and preferably 2.0 or less, more preferably 1.75 or less, still more preferably 1.5 or less, still more preferably 1.4 or 1.40 or less, particularly preferably 1.3 or less, where the ratio of the amount of the component (B) to the amount of the curing agent is a, the ratio of the amount of the component (B) to the amount of the component (C) to the amount of the reactive group equivalent is a. By making the amount ratio of the epoxy resin to the curing agent within the range, the effect of the present invention can be easily obtained.
The content of the other curing agent (F) in the resin composition may be 0% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1.0% by mass or more, more preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably 5% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition.
The content of the other curing agent (F) in the resin composition may be 0% by mass or more, preferably 0.1% by mass or more, more preferably 1.0% by mass or more, particularly preferably 5.0% by mass or more, more preferably 50% by mass or less, more preferably 20% by mass or less, particularly preferably 10% by mass, based on 100% by mass of the resin component in the resin composition.
(G) curing accelerator
The resin composition of the present invention may contain (G) a curing accelerator as an optional component.
Examples of the curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. (G) The curing accelerator may be used alone or in combination of 1 or more than 2.
Examples of the phosphorus-based curing accelerator include: aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hexahydrophthalate hydrogen, tetrabutylphosphonium 2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenoxy, 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-tolyl borate, tetraphenyl phosphonium tetraphenyl borate, tetraphenyl phosphonium tetra-p-tolyl borate, triphenylethyl phosphonium tetraphenyl borate, tris (3-methylphenyl) ethyl phosphonium tetraphenyl borate, tris (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylphenyl) triphenyl phosphonium thiocyanate, tetraphenyl phosphonium thiocyanate, butyltriphenyl phosphonium thiocyanate, and the like; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactant; aliphatic phosphines such as tributylphosphine, tri-t-butylphosphine, trioctylphosphine, di-t-butyl (2-butenyl) phosphine, di-t-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutyl phenyl phosphine, di-tert-butyl phenyl phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, butyl diphenyl phosphine, diphenyl cyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-tert-butylphenyl) phosphine, tri (2, 4-dimethylphenyl) phosphine, tri (2, 5-dimethylphenyl) phosphine, tri (2, 6-dimethylphenyl) phosphine, tri (3, 5-dimethylphenyl) phosphine, tri (2, 4, 6-trimethylphenyl) phosphine, tri (2, 6-dimethyl-4-ethoxyphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-ethoxyphenyl) phosphine, tri (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenyl) phosphino-ethane, 1, 3-bis (diphenyl) phosphine, 2 '-diphenyl) phosphine, bis (2, 2' -diphenyl) phosphine, bis (2, 2-diphenyl) phosphine, etc.
Examples of urea curing accelerators include: 1, 1-dimethylurea; aliphatic dimethylureas such as 1, 3-trimethylurea, 3-ethyl-1, 1-dimethylurea, 3-cyclohexyl-1, 1-dimethylurea, and 3-cyclooctyl-1, 1-dimethylurea; 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 ' -dimethyltoluene) urea, etc.
Examples of the guanidine curing accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1-dimethylbiguanide, 1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and the like.
Examples of the imidazole-based curing accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate adduct, and process for preparing the same, imidazole compounds such as 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.
As the imidazole curing accelerator, commercially available products can 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 metal-based curing accelerator include: organometallic complexes or salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin, and the like. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate; organic copper complexes such as copper (II) acetylacetonate; organic zinc complexes such as zinc acetylacetonate (II); organic iron complexes such as iron (III) acetylacetonate; organonickel complexes such as nickel (II) acetylacetonate; 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.
Examples of the amine curing accelerator include: trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, 1, 8-diazabicyclo (5, 4, 0) -undecene, and the like.
As the amine curing accelerator, commercially available ones can be used, and examples thereof include "MY-25" manufactured by Ajinomoto Fine-Techno Co., ltd.
The content of the (G) curing accelerator in the resin composition is not particularly limited, but is preferably 15 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, particularly preferably 3 mass% or less, based on 100 mass% of the nonvolatile component in the resin composition. The lower limit of the content of the (G) curing accelerator in the resin composition is not particularly limited, and when the nonvolatile component in the resin composition is set to 100 mass%, it may be, for example, 0 mass% or more, 0.001 mass% or more, 0.01 mass% or more, 0.1 mass% or more, 0.5 mass% or more, or the like.
(H) other additives
Any additive may be further contained as a nonvolatile component in the resin composition of the present invention. Examples of such additives include: radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; phenolic curing agents (phenol curing agents), naphthol curing agents, acid anhydride curing agents, thiol curing agents, benzoxazine curing agents, cyanate curing agents, carbodiimide curing agents, imidazole curing agents, and other epoxy curing agents other than active ester compounds; thermoplastic resins such as phenoxy resin, polyvinyl acetal resin, polyolefin resin, polysulfone resin, polyether sulfone resin, polyphenylene oxide resin, polycarbonate resin, polyether ether ketone resin, and polyester resin; organic fillers such as rubber particles; organocopper compounds, organozinc compounds, organocobalt compounds, and other organometallic compounds; 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; defoamers such as silicone defoamers, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; an adhesion improver such as urea silane; adhesion-imparting agents such as triazole-based adhesion-imparting agents, tetrazole-based adhesion-imparting agents, and triazine-based adhesion-imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus flame retardants (e.g., phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide); a dispersant such as a phosphate dispersant, a polyoxyalkylene dispersant, an alkyne dispersant, a silicone dispersant, an anionic dispersant, and a cationic dispersant; boric acid ester stabilizer, titanate stabilizer, aluminate stabilizer, zirconate stabilizer, isocyanate stabilizer, carboxylic acid stabilizer, carboxylic anhydride stabilizer, etc. (H) The other additives may be used alone in 1 kind, or may be used in combination in an arbitrary ratio of 2 or more kinds. The content of the other additive (H) may be appropriately set by those skilled in the art.
[ (K) organic solvent ]
The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above-mentioned nonvolatile components. As the organic solvent (K), a known organic solvent may be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (K) 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, and diphenyl ether; 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, methyl methoxypropionate, and the like; 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. (K) The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds in an arbitrary ratio.
In one embodiment, the content of the (K) organic solvent is not particularly limited, and may be, for example, 60 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, 10 mass% or less, or the like, when the total content of the components in the resin composition is 100 mass%.
Method for producing resin composition
The resin composition of the present invention can be produced, for example, as follows: to an arbitrary preparation vessel, (A) an organic filler having liquid crystallinity, (B) an epoxy resin, and (C) an active ester compound, (D) an inorganic filler, and (E) a radical polymerizable compound, and (F) other curing agents, and (G) a curing accelerator, and (H) other additives, and (K) an organic solvent, and mixing them in an arbitrary order and/or partially or all at the same time. 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. Further, the resin composition may be uniformly dispersed by stirring or shaking with a stirring device such as a mixer or a shaking device during or after the addition and mixing. In addition, the defoaming may be performed under low pressure conditions such as vacuum while stirring or shaking.
< Properties of resin composition >
The resin composition of the present invention comprises (A) an organic filler having liquid crystallinity, (B) an epoxy resin, and (C) an active ester compound. By using such a resin composition, a cured product having a low dielectric loss tangent even in a high-temperature environment such as 90 ℃ and excellent crack resistance after the stain removal treatment can be obtained, and a cured product having a low dielectric loss tangent even in a room temperature or normal temperature region such as 23 ℃ can be obtained.
The cured product of the resin composition of the present invention may have a feature of being able to suppress the occurrence of cracks after the desmutting treatment (roughening treatment). Therefore, in one embodiment, when a circuit board is manufactured and treated for contamination removal as in test example 2 below, and then 100 copper pad (copper pad) portions of the circuit board are observed, the number of cracks may be preferably 10 or less (10% or less).
The cured product of the resin composition of the present invention may have a characteristic that the dielectric loss tangent (Df) is low even in a high-temperature environment such as 90 ℃. Accordingly, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition when measured at 5.8GHz and 90 ℃ as in test example 1 below may be preferably 0.020 or less, more preferably 0.010 or less, still more preferably 0.009 or less, still more preferably 0.007 or less, 0.006 or less, particularly preferably 0.005 or less, 0.004 or less, and 0.003 or less.
The cured product of the resin composition of the present invention may have a characteristic that the dielectric loss tangent (Df) is also low at room temperature or normal temperature such as 23 ℃. Therefore, in one embodiment, the dielectric loss tangent (Df) of the cured product of the resin composition as measured at 5.8GHz and 23℃in the following test example 1 may be preferably 0.020 or less, more preferably 0.010 or less, still more preferably 0.009 or less, still more preferably 0.007 or less, still more preferably 0.006 or less, still more preferably 0.005 or less, 0.004 or less, particularly preferably 0.003 or less, and 0.002 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, it can be suitably used as: a resin composition for forming an insulating layer (insulating layer forming resin composition for forming a conductor layer) which is an insulating layer for forming a conductor layer (including a rewiring layer) formed on the insulating layer. In the printed wiring board described later, the resin composition may 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 widely used in 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, in the case of manufacturing a semiconductor chip package 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 forming layer (a resin composition for forming a re-wiring forming layer) 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). When 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 off, and a method of manufacturing the same
(6) And forming a rewiring layer as a conductor layer on the rewiring layer.
The resin composition of the present invention can provide an insulating layer having excellent embedding properties, and therefore 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 can be used by coating in the form of a varnish, and is generally preferably used in the form of a sheet laminate containing the resin composition in industry.
As the sheet-like laminate, a resin sheet or a prepreg shown below is preferable.
In one embodiment, the resin sheet comprises 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 viewpoint of reducing the thickness of the printed wiring board and providing a cured product of the resin composition which has excellent insulation even when it 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 and 10 μm or more.
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 low-cost polyethylene terephthalate is particularly preferable.
In the case of using a metal foil as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil formed of a single metal of copper may be used, or a foil formed of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.
The support may be subjected to a matte treatment, a corona discharge 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. The support with a release layer may be a commercially available support, and examples thereof include: examples of the release layer include "SK-1", "AL-5", "AL-7", LUMIRROR T60", purex", and "Unipel", you Niji ", which are obtained from Wako Co., ltd.
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 that is 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, as follows: the resin composition layer is formed by directly preparing a liquid resin composition or preparing a resin varnish obtained by dissolving the resin composition in an organic solvent, applying the resin varnish to a support by using a die coater or the like, and drying the resin varnish.
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 hot air blowing. The drying conditions are not particularly limited, and the drying is performed under such conditions that the content of the organic solvent in the resin composition layer becomes 10 mass% or less, preferably 5 mass% or less. The resin composition layer may be formed by drying at 50 to 150 ℃ for 3 to 10 minutes, for example, in the case of using a resin composition or a resin varnish containing 30 to 60 mass% of an organic solvent, depending on the boiling point of the organic solvent in the resin composition or the resin varnish.
The resin sheet may be wound into a roll and stored. In the case where 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 base material with the resin composition of the present invention.
The sheet-like fibrous base material used for the prepreg is not particularly limited, and glass cloth, aramid nonwoven fabric, liquid crystal polymer nonwoven fabric, or the like, which is generally used as a base material for the prepreg, can be used. From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the sheet-like fibrous base material is preferably 50 μm or less, more preferably 40 μm or less, 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.
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 following steps (I) and (II) using the resin sheet described above:
(I) And (II) a step of laminating the resin sheet on the inner substrate so that the resin composition layer of the resin sheet is bonded to the inner substrate, and (II) a step of curing (e.g., thermally curing) the resin composition layer to form an insulating layer.
The "inner substrate" used in the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene oxide 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 subjected to patterning. 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, an intermediate product to be further formed into an insulating layer and/or a conductor layer in the production of a printed wiring board is also included in the "inner layer substrate" referred to 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 layer substrate and the resin sheet can be performed by, for example, thermally pressing the resin sheet to the inner layer substrate from the support side. As a member for heat-press bonding the resin sheet to the inner layer substrate (hereinafter, sometimes referred to as "heat-press bonding member"), for example, a heated metal plate (SUS end plate or the like), a metal roller (SUS roller) or the like can be cited. It is preferable that the resin sheet is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently conforms to the surface irregularities of the inner layer substrate, without directly pressing the thermocompression bonding member against the resin sheet.
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 80℃to 140℃and the heat press-bonding pressure is preferably in the range of 0.098MPa to 1.77MPa and more preferably 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 30 seconds to 300 seconds. The lamination is preferably performed under reduced pressure of 26.7hPa or less.
Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by the company name machine, vacuum applicators manufactured by Nikko-Materials, and batch vacuum pressurized laminators.
After lamination, the laminated resin sheet may 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 the same as those for the above-described lamination under heat and pressure. The smoothing treatment may be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the commercially available vacuum laminator described above.
The support may be removed between the step (I) and the step (II), or may be removed after the step (II).
In the step (II), the resin composition layer is cured (for example, thermally cured) to form an insulating layer formed of a cured product of the resin composition. The curing conditions of the resin composition layer are not particularly limited, and those generally used in forming an insulating layer of a printed wiring board can be used.
For example, the heat curing condition of the resin composition layer varies depending on the kind of the resin composition, and in one embodiment, the curing temperature is, for example, 120 ℃ or higher, 130 ℃ or higher, 135 ℃ or higher, preferably 140 ℃ or higher, more preferably 150 ℃ or higher, still more preferably 170 ℃ or higher, and is, for example, 240 ℃ or lower, preferably 220 ℃ or lower, and still more preferably 210 ℃ or lower. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, still more preferably 15 minutes to 100 minutes.
The resin composition layer may be preheated at a temperature lower than the curing temperature before the resin composition layer is thermally cured. For example, the resin composition layer may be preheated for 5 minutes or more, preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, still more preferably 15 minutes to 100 minutes at a temperature of 50℃to 140℃and preferably 60℃to 135℃and more preferably 70℃to 130℃before the resin composition layer is thermally cured.
In the case of manufacturing a printed wiring board, (III) a step of forming a hole in the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be further performed. These steps (III) to (V) can be performed according to various methods known to those skilled in the art for producing printed wiring boards. In the case where the support is removed after the step (II), the removal of the support may be performed between the step (II) and the step (III), between the step (III) and the step (IV), or between the step (IV) and the step (V). The insulating layer and the conductor layer in the steps (II) to (V) may be formed repeatedly as necessary to form a multilayer wiring board.
In other embodiments, the printed wiring board of the present invention may be manufactured using the prepreg described above. The manufacturing 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, such as a via hole or a via hole, by forming the hole in the insulating layer. The step (III) may be performed using, for example, a drill, a laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer, or the like. The size and shape of the holes may be appropriately determined according to the design of the printed wiring board.
The step (IV) is a step of roughening the insulating layer. In general, in this step (IV), the removal of the contamination is also performed. The step and condition of the roughening treatment are not particularly limited, and known steps and conditions 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 neutralization 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 Anmeite Japan Co., ltd. 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 controlling the swelling of the resin of the insulating layer to an appropriate level, it is preferable to impregnate the insulating layer with 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 Anmei Japanese Kogyo Co., ltd.
The neutralizing liquid used in the roughening treatment is preferably an acidic aqueous solution, and examples of the commercial product include "Reduction Solution Securiganth P" manufactured by Anmei Japanese Co., ltd.
The treatment with the neutralizing solution may be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ℃ for 5 to 30 minutes. From the viewpoint of handling, the object to be roughened with an oxidizing agent is preferably immersed in a neutralization solution at 40 to 70 ℃ for 5 to 20 minutes.
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 for the conductor layer is not particularly limited.
In a preferred embodiment, the conductor layer contains 1 or more metals selected from 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 metals (for example, a nickel-chromium alloy, a copper-nickel alloy, and a copper-titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel-chromium alloy is preferable from the viewpoints of versatility of conductor layer formation, cost, ease of pattern formation, and the like.
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. In the case where the conductor layer has a multilayer structure, the layer to be connected to 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 varies depending on the design of the desired printed wiring board, but is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.
In one embodiment, the conductor layer may be formed by plating. For example, the surface of the insulating layer may be plated by a conventionally known technique such as a half-addition method or a full-addition method to form a conductor layer having a desired wiring pattern, and it is preferably formed by a half-addition method from the viewpoint of ease of production. 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 is formed on the formed plating seed layer so as to expose a part of the plating seed layer in accordance with a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electrolytic plating, 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 another embodiment, the conductor layer may be formed using a metal foil. When the conductor layer is formed using a metal foil, the step (V) is preferably performed between the step (I) and the step (II). For example, after the step (I), the support is removed, and a metal foil is laminated on the surface of the exposed resin composition layer. Lamination of the resin composition layer and the metal foil may be performed by a vacuum lamination method. The lamination conditions may be the same as those described for the step (I). Next, step (II) is performed to form an insulating layer. Then, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method or a modified semi-additive method using a metal foil on the insulating layer.
The metal foil can be produced by a known method such as electrolysis or rolling. Examples of the commercial products of the metal foil include HLP foil, JXUT-III foil, 3EC-III foil, TP-III foil, etc. manufactured by JX Nitshi metal Co., ltd.
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, two-wheeled motor vehicles, automobiles, electric trains, ships, aircraft, and the like).
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to these examples. In the following, unless otherwise indicated, "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 (25 ℃).
Synthesis example 1: synthesis of liquid Crystal Polymer
To a polymerization vessel having stirring vanes, 60 mol% of 6-hydroxy-2-naphthoic acid (HNA), 20 mol% of 4, 4-dihydroxybiphenyl (BP), 15.5 mol% of terephthalic acid (TPA) and 4.5 mol% of 2, 6-naphthalenedicarboxylic acid (NADA) were added, potassium acetate and magnesium acetate were added as catalysts, the polymerization vessel was subjected to nitrogen substitution by performing pressure reduction-nitrogen injection 3 times, acetic anhydride (1.08 molar equivalent to hydroxyl group) was further added, and the temperature was raised to 150 ℃ and the acetylation was performed in a reflux state for 2 hours.
After the completion of the acetylation, the polymerization vessel in the acetic acid distillation state was heated at 0.5℃per minute, and when the melt temperature in the vessel reached 310℃the polymer was taken out and cooled to solidify. The obtained polymer was pulverized to a size passing through a sieve having a pore diameter of 2.0mm to obtain a prepolymer.
Then, the prepolymer obtained above was heated from room temperature to 310℃for 14 hours by a heater in an oven manufactured by Daiki Kagaku (Yamato Scientific), and then was kept at 310℃for 1 hour to carry out solid-phase polymerization. Then, the heat was naturally dissipated at room temperature to obtain a liquid crystal polymer a. The liquid crystal polymer A was melted by heating on a microscope heating stage using a polarization microscope (trade name: BH-2) manufactured by Olympic Co., ltd. Having a microscope heating stage (hot stage) (trade name: FP82 HT) manufactured by Metler-tolido (METLER), and the presence or absence of optical anisotropy was confirmed to exhibit liquid crystallinity.
Preparation example 1: manufacturing of liquid Crystal Polymer particles
The powder of the liquid crystal polymer A synthesized in the above was continuously pulverized using a device obtained by combining SPK-12 jet mill (jet mill) manufactured by Japanese pneumatic Industrial Co., ltd. (Nippon Pneumatic Kogyo) with DSF-10 classifier manufactured by Co., ltd.) under a pulverizing pressure of 0.65MPa at a resin supply amount of 5kg/h to obtain liquid crystal polymer particles A.
< evaluation of liquid Crystal Polymer particles >
(determination of melting Point)
The melting point of the liquid crystal polymer particles A obtained above was measured by a Differential Scanning Calorimeter (DSC) manufactured by Hitachi High-Tech Science Co., ltd, in accordance with the test method of ISO11357 and ASTM D3418. At this time, the temperature was raised from room temperature to 360 to 380 ℃ at a heating rate of 10 ℃/min, after which the polymer was completely melted, the temperature was lowered to 30 ℃ at a rate of 10 ℃/min, and the peak of the endothermic peak obtained when the temperature was raised to 380 ℃ at a rate of 10 ℃/min was used as the melting point. The melting point measured was 319 ℃.
(determination of particle size distribution)
The particle size distribution of the liquid crystal polymer particles A obtained in the above was measured by using a laser diffraction scattering particle size distribution measuring apparatus (LS 13320 dry system, manufactured by Beckman Coulter, inc.), and a Tornado dry powder module (Tornado Dry Powder Module) was mounted. D50, D90 and Dp, which are parameters showing the particle size distribution, are obtained as calculation results from the measurement data. As a result, the D50 was 4.8. Mu.m, and the D90/D50 was 1.7.
(measurement of dielectric loss tangent (10 GHz))
Using the liquid crystal polymer particles A obtained in the above, they were heated and melted at a temperature of from the melting point to +30℃, and injection-molded with a mold having a thickness of 30 mm. Times.30 mm. Times.0.4 mm, to prepare a flat-plate-shaped test piece. Next, using the flat plate-like test piece, the dielectric loss tangent at a frequency of 10GHz was measured by a separation column dielectric resonator method (SPDR method, split Post Dielectric Resonator) using a network analyzer N5247A, which is a company of dect technology (Keysight Technologies). The dielectric loss tangent was measured at n=4 for each sample, and was found to be 0.0007 as an average value of 4 times.
(determination of released gas)
The liquid-crystalline polymer particles A obtained in the above were placed in a 20ml vial and sealed, and then subjected to heat treatment at 190℃for 1 hour. The gases of acetic acid and other gases (phenol and phenyl acetate) generated by the heat treatment were quantified by gas chromatography (HP 7820A) to which a head space sampler (HP 7697A) manufactured by Hewlett Packard company was connected. The column was measured using a FID detector using G-100 (40 m) from the chemical examination Association, with other conditions set at an initial temperature of 45℃and a heating rate of 20℃per minute, a final temperature of 280℃and a helium pressure of 8.3psi and a split ratio of 2.0. Acetic acid was measured as a released gas at 0.4ppm and the other released gases at 5.8ppm.
Examples 1 to 8 and comparative example 1: preparation of resin varnish
Example 1
15 parts of naphthalene type epoxy resin (HP-4032-SS, manufactured by DIC Co., ltd., epoxy equivalent 144 g/eq.), 43 parts of an active ester type curing agent (HPC-8150-62T, active group equivalent 229g/eq., toluene solution containing 61.5 mass% of nonvolatile components), 5 parts of other curing agents (phenol type curing agent, manufactured by DIC Co., ltd. "LA-3018-50P", hydroxyl equivalent 151g/eq., 1-methoxy-2-propanol solution containing 50 mass% of nonvolatile components), 2 parts of liquid crystal polymer powder A as component (A), and spherical silica (SO-C2, average particle diameter 0.5 μm, specific surface area 5.8 m) surface-treated with an amine type alkoxysilane compound (KBM 573, manufactured by Xinyue chemical Co., ltd.) as component 2 125 parts of a curing accelerator (manufactured by Kagaku Co., ltd., "1B2 PZ"), 10 parts of MEK, 10 parts of cyclohexanone were mixed and uniformly dispersed by a high-speed rotary mixer to obtain a resin varnish.
Example 2
In example 1, 2 parts of a MEK solution (nonvolatile matter 62 mass%) of a maleimide compound a (Mw/mn=1.81, t "=1.47 (mainly 1, 2 or 3)) represented by the following formula (M) synthesized by the method described in synthesis example 1 of japanese patent application laid-open technical bulletin No. 2020-500211 was further used. A resin varnish was obtained in the same manner as in example 1 except for the above matters;
[ chemical formula 1]
Example 3
A resin varnish was obtained in the same manner as in example 1 except that 2 parts of another maleimide compound (MIR-5000-60T, manufactured by Kagaku Co., ltd., nonvolatile matter 60% by mass in toluene) was added in example 1.
Example 4
A resin varnish was obtained in the same manner as in example 1 except that 2 parts of another maleimide compound (MIR-3000-70 MT, manufactured by Kagaku Co., ltd., nonvolatile matter 70% by mass of toluene/MEK mixed solution) was added in example 1.
Example 5
A resin varnish was obtained in the same manner as in example 1, except that 2 parts of another maleimide compound (BMI-689, manufactured by design molecular Co., ltd.) was added to example 1.
Example 6
A resin varnish was obtained in the same manner as in example 1 except that 2 parts by weight of another compound having a double bond (OPE-2 St-1200, manufactured by Mitsubishi gas chemical Co., ltd., nonvolatile matter was added to the mixture of the compound and toluene in an amount of 65% by mass).
Example 7
A resin varnish was obtained in the same manner as in example 1, except that 2 parts of the liquid crystal polymer powder a as the component (a) was changed to 1 part in example 1.
Example 8
A resin varnish was obtained in the same manner as in example 1, except that the liquid crystal polymer powder a as the component (a) was changed from 2 parts to 4 parts in example 1.
Comparative example 1
A resin varnish was obtained in the same manner as in example 1, except that 2 parts of the liquid crystal polymer powder a as the component (a) was not added in example 1.
Preparation example 1: production of resin sheet A having a thickness of 40 μm as a layer of the resin composition
As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke Co., ltd., thickness: 38 μm) having a release layer was prepared. The resin varnishes obtained in examples and comparative examples were uniformly applied to the release layer of the support under the condition that the thickness of the dried resin composition layer became 40. Mu.m. Then, the resin composition was dried at 80 to 100 ℃ (average 90 ℃) for 4 minutes to obtain a resin sheet a comprising a support and a resin composition layer.
Test example 1: determination of dielectric loss tangent
Using the resin varnishes obtained in examples and comparative examples, the resin sheet a obtained in production example 1 was cured in an oven at 190 ℃ for 90 minutes. The support was peeled from the resin sheet a taken out from the oven, thereby obtaining a cured product of the resin composition layer. The cured product was cut out to have a length of 80mm and a width of 2mm, and was used as a cured product for evaluation.
For each cured product for evaluation, the dielectric loss tangent (Df value) was measured by the cavity perturbation method at a measurement frequency of 5.8GHz, and at a measurement temperature of 23℃and 90℃using "HP8362B" manufactured by Agilent technologies (Agilent Technologies), inc. The average value of the 2 test pieces was calculated by measuring them.
Preparation example 2: preparation of resin sheet B having a thickness of 25 μm as a layer of the resin composition
As a support, a polyethylene terephthalate film (AL 5, manufactured by Lindeke Co., ltd., thickness: 38 μm) having a release layer was prepared. The resin varnishes obtained in examples and comparative examples were uniformly applied onto the release layer of the support under such conditions that the thickness of the dried resin composition layer became 25. Mu.m, and dried at 70℃to 80℃for 2.5 minutes to obtain a resin sheet B comprising the support and the resin composition layer.
Test example 2: evaluation of crack resistance after stain removal treatment
The resin sheet B having a thickness of 25 μm produced in production example 2 was laminated on both surfaces of the inner layer substrate by bonding a resin composition layer to the inner layer substrate, using a batch vacuum pressure laminator (Nikko-Materials Co., ltd. 2-stage lamination laminator "CVP 700"), on both surfaces of a core material (E705 GR, manufactured by Hitachi chemical Co., ltd., thickness 400 μm) having a circular copper pad (copper thickness of 35 μm) having a diameter of 350 μm formed in a lattice shape at intervals of 400 μm under the condition of reaching a copper residue ratio of 60%. The lamination is carried out as follows: after the pressure was reduced to 13hPa or less for 30 seconds, the mixture was pressure-bonded at 100℃under a pressure of 0.74MPa for 30 seconds. Putting it into a 130 ℃ oven for heating for 30 minutesClock, then move to 170 ℃ oven heating for 30 minutes. The support was further peeled off, and the obtained circuit board was immersed in Swelling Dip Securiganth P of Anmei Japanese Co., ltd., as a swelling liquid, at 60℃for 10 minutes. Next, the mixture was subjected to a roughening treatment in an aqueous solution of Concentrate Compact P (KMnO 4 :60g/L, naOH:40g/L in water) was immersed in the solution at 80℃for 30 minutes. Finally, the resultant solution was immersed in Reduction solution Securiganth P made by Anmei Japanese Co., ltd. As a neutralizing solution at 40℃for 5 minutes. The copper pad portions of the circuit board after 100 roughening treatments were observed to confirm the presence or absence of cracks in the resin composition layer. If the number of cracks is 10 or less, it is determined as good, and if it is more than 10, it is determined as x.
The amounts (parts by mass) of the volatile components (a) to (G) used in the resin compositions of examples and comparative examples and the measurement results of the test examples are shown in table 1 below. In table 1, the nonvolatile components (mass%) of each component are shown in the column "n.v.".
TABLE 1
From the above, it was found that by using a resin composition containing (a) an organic filler having liquid crystallinity, (B) an epoxy resin, and (B) an active ester compound, a cured product having a low dielectric loss tangent (Df) even in a high-temperature environment such as 90 ℃ and excellent crack resistance after a stain removal treatment can be obtained. It is also found that the cured product has a low dielectric loss tangent (Df) even at room temperature or a room temperature range such as 23 ℃.

Claims (11)

1. A resin composition comprising (A) an organic filler having liquid crystallinity, (B) an epoxy resin and (C) an active ester compound.
2. The resin composition according to claim 1, wherein the content of the component (A) is 0.1% by mass or more and 10% by mass or less, based on 100% by mass of the resin component in the resin composition.
3. The resin composition according to claim 1, wherein the melting point of the organic filler (A) having liquid crystallinity is 270 ℃ or higher.
4. The resin composition according to claim 1, further comprising (D) an inorganic filler.
5. The resin composition according to claim 1, further comprising (E) a radical polymerizable compound.
6. The resin composition according to claim 1, which is used for forming an interlayer insulating layer of a printed wiring board.
7. A cured product of the resin composition according to any one of claims 1 to 6.
8. A sheet laminate comprising the resin composition according to any one of claims 1 to 6.
9. A resin sheet, comprising:
support body
A resin composition layer comprising the resin composition according to any one of claims 1 to 6, which is provided on the support.
10. A printed wiring board comprising an insulating layer formed of the cured product of the resin composition according to any one of claims 1 to 6.
11. A semiconductor device comprising the printed wiring board according to claim 10.
CN202311305747.3A 2022-10-14 2023-10-10 Resin composition Pending CN117887207A (en)

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