CN114163772A - Resin composition - Google Patents

Resin composition Download PDF

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Publication number
CN114163772A
CN114163772A CN202111063372.5A CN202111063372A CN114163772A CN 114163772 A CN114163772 A CN 114163772A CN 202111063372 A CN202111063372 A CN 202111063372A CN 114163772 A CN114163772 A CN 114163772A
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China
Prior art keywords
resin composition
mass
resin
component
composition according
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CN202111063372.5A
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Chinese (zh)
Inventor
中村洋介
渡边真俊
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Ajinomoto Co Inc
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Ajinomoto Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B32B3/085—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts spaced apart pieces on the surface of a layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/036—Multilayers with layers of different types
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08J2363/00—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
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Abstract

[ problem ] to provide a resin composition for obtaining a cured product that can suppress the occurrence of cracks while maintaining a high reflectance. [ solution ] A resin composition comprising (A) an epoxy resin, (B) a white inorganic pigment and (C) silica, wherein the total content of the components (B) and (C) is 70% by mass or less, assuming that 100% by mass of nonvolatile components are contained in the resin composition.

Description

Resin composition
Technical Field
The present invention relates to a resin composition. Further, the present invention relates to a cured product, a resin sheet, a reflective sheet and a printed wiring board obtained using the resin composition.
Background
Printed circuit boards are increasingly used in applications where Light Emitting Diodes (LEDs) that emit light at low power, such as backlights for liquid crystal displays of mobile terminals, computers, televisions, and the like, and light sources for lighting fixtures, are directly mounted.
A reflective sheet for reflecting light is formed on the outermost layer of such a printed circuit board in order to improve the efficiency of extracting light emitted from the light source.
The resin composition for use in the reflective sheet generally contains titanium oxide or the like as an inorganic filler. As a method for improving the reflectance, a method of increasing the content of titanium oxide as much as possible is known (patent document 1). However, there are problems as follows: when the content of titanium oxide is increased, the toughness of the cured coating film obtained from the resin composition is lowered, and the occurrence of cracks is increased.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-529551.
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing a resin composition for obtaining a cured product that can suppress the occurrence of cracks while maintaining a high reflectance.
Means for solving the problems
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that: the present inventors have found that a cured product which can suppress the occurrence of cracks while maintaining a high reflectance can be obtained unexpectedly by using a resin composition containing (a) an epoxy resin, (B) a white inorganic pigment, and (C) silica, and the total content of (B) the white inorganic pigment and (C) silica being 70% by mass or less.
That is, the present invention includes the following.
[1] A resin composition comprising (A) an epoxy resin, (B) a white inorganic pigment, and (C) silica,
the total content of the component (B) and the component (C) is 70% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
[2] The resin composition according to [1], wherein the component (A) comprises (A-1) an epoxy resin which is solid at a temperature of 25 ℃.
[3] The resin composition according to the above [1] or [2], wherein the total content of the component (B) and the component (C) is 30% by mass or more, assuming that the nonvolatile component in the resin composition is 100% by mass.
[4] The resin composition according to any one of the above [1] to [3], wherein the mass ratio of the component (C) to the component (B) (mass of component (C)/(mass of component (B)) is 0.2 to 5.0.
[5] The resin composition according to any one of the above [1] to [4], wherein the component (B) is selected from the group consisting of alumina, titania, zirconia, magnesia, barium titanate, zinc oxide, cerium oxide and calcium carbonate.
[6] The resin composition according to any one of the above [1] to [5], further comprising (D) a thermoplastic resin.
[7] The resin composition according to [6], wherein the weight-average molecular weight of the component (D) is 10,000 or more.
[8] The resin composition according to the above [6] or [7], wherein the component (D) is a thermoplastic resin having a transmittance of 80% or more for light having a wavelength of 450nm incident on the film surface when the film is formed into a film of 20 μm in the vertical direction.
[9] The resin composition according to any one of the above [6] to [8], wherein the component (D) is selected from a phenoxy resin, an acrylic resin and a polyphenylene ether resin.
[10] The resin composition according to any one of the above [1] to [9], wherein the content of the component (A) is 10% by mass to 35% by mass, assuming that the nonvolatile component in the resin composition is 100% by mass.
[11] The resin composition according to any one of the above [1] to [10], wherein the content of the component (B) is 25% by mass to 40% by mass, assuming that the nonvolatile component in the resin composition is 100% by mass.
[12] The resin composition according to any one of the above [1] to [11], wherein the content of the component (C) is 15% by mass to 35% by mass, assuming that 100% by mass of nonvolatile components in the resin composition are present.
[13] The resin composition according to any one of [1] to [12], wherein the mass ratio of the component (A) to the total of the components (B) and (C), (the mass of the component (A)/(the mass of the components (B)) and (C)), is 0.1 to 1.0.
[14] The resin composition according to any one of the above [1] to [13], wherein an elongation of a cured product of the resin composition measured at 25 ℃ according to JIS K7161 is 2% or more.
[15] The resin composition according to any one of the above [1] to [14], which is used for light reflection.
[16] A cured product of the resin composition according to any one of [1] to [15 ].
[17] A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of [1] to [15 ].
[18] A reflective sheet comprising a cured product of the resin composition according to any one of [1] to [15 ].
[19] A printed wiring board comprising the reflection sheet according to [18] above as an interlayer insulating layer or a solder resist layer.
Effects of the invention
According to the resin composition of the present invention, a cured product in which the occurrence of cracks can be suppressed while maintaining a high reflectance can be obtained.
Drawings
Fig. 1 is a schematic cross-sectional view showing an example of a printed wiring board.
Detailed Description
The present invention will be described in detail below with reference to preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be carried out by arbitrarily changing the embodiments without departing from the scope of the claims and the equivalent scope of the present invention.
[ resin composition ]
The resin composition of the present invention contains (A) an epoxy resin, (B) a white inorganic pigment, and (C) silica, and the total content of the (B) white inorganic pigment and the (C) silica is 70% by mass or less. By using such a resin composition, a cured product can be obtained in which the occurrence of cracks can be suppressed while maintaining a high reflectance.
The resin composition may further contain an optional component in addition to the epoxy resin (a), the white inorganic pigment (B), and the silica (C). Examples of the optional components include (D) a thermoplastic resin, (E) a curing agent, (F) a curing accelerator, (G) other additives, and (H) an organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.
< epoxy resin (A) >
The resin composition of the present invention contains (a) an epoxy resin. (A) The epoxy resin means a curable resin having an epoxy group. (A) The epoxy resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the epoxy resin (A) include a bixylenol-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 hydrogenated bisphenol A-type epoxy resin, a dicyclopentadiene-type epoxy resin, a triphenol-type epoxy resin, a naphthol novolac-type epoxy resin, a phenol novolac-type epoxy resin, a tert-butyl-catechol-type epoxy resin, a naphthalene-type epoxy resin, a naphthol-type epoxy resin, an anthracene-type epoxy resin, a glycidylamine-type epoxy resin, a glycidyl ester-type epoxy resin, a cresol novolac-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, an alicyclic epoxy resin, a heterocyclic epoxy resin, an epoxy resin having a spiro ring, Cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthalene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenol phthalimidine type epoxy resin, phenolphthalein type epoxy resin, and the like.
In the resin composition, the epoxy resin (a) preferably contains an epoxy resin having 2 or more epoxy groups in 1 molecule. The proportion of the epoxy resin having 2 or more epoxy groups in 1 molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, relative to 100% by mass of the nonvolatile component of the epoxy resin (a).
The epoxy resin includes (A-1) an epoxy resin that is solid at a temperature of 25 ℃ (hereinafter sometimes referred to as "solid epoxy resin") and (A-2) an epoxy resin that is liquid at a temperature of 25 ℃ (hereinafter sometimes referred to as "liquid epoxy resin"). In the resin composition of the present invention, the epoxy resin (a) may be composed of only the solid epoxy resin (a-1), only the liquid epoxy resin (a-2), or a combination of the solid epoxy resin (a-1) and the liquid epoxy resin (a-2).
The solid epoxy resin (a-1) is preferably a solid epoxy resin having 3 or more epoxy groups in 1 molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in 1 molecule.
The solid epoxy resin (a-1) is preferably a bixylenol 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 tetraphenylethane type epoxy resin, a phenol phthalimidine type epoxy resin, or a phenolphthalein type epoxy resin.
Specific examples of the solid epoxy resin (A-1) include "HP 4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resins) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC; "N-695" (cresol novolac type epoxy resin) manufactured by DIC; "HP-7200", "HP-7200 HH", "HP-7200H" and "HP-7200L" (dicyclopentadiene type epoxy resins) manufactured by DIC; "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" and "HP 6000" (naphthalene ether type epoxy resins) manufactured by DIC; EPPN-502H (triphenol type epoxy resin) manufactured by Nippon chemical Co., Ltd.; "NC 7000L" (naphthol novolac type epoxy resin) manufactured by japan chemicals); "NC 3000H", "NC 3000L", "NC 3000 FH" and "NC 3100" (biphenyl type epoxy resin) manufactured by japan chemical company; ESN475V (naphthalene type epoxy resin) manufactured by Nippon iron ケミカル & マテリアル; "ESN 485" (naphthol type epoxy resin) manufactured by Nippon iron ケミカル & マテリアル Co., Ltd.; ESN375 (dihydroxynaphthalene-type epoxy resin) manufactured by Nippon iron ケミカル & マテリアル Co., Ltd.; "YX 4000H", "YX 4000 HK" and "YL 7890" (bixylenol type epoxy resin) manufactured by mitsubishi ケミカル; "YL 6121" (biphenyl type epoxy resin) manufactured by Mitsubishi ケミカル; "YX 8800" (anthracene-based epoxy resin) manufactured by Mitsubishi ケミカル; "YX 7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi ケミカル Co., Ltd.; PG-100 and CG-500 manufactured by Osaka ガ ス ケミカル company; "YX 7760" (bisphenol AF type epoxy resin) manufactured by mitsubishi ケミカル corporation; "YL 7800" (fluorene-based epoxy resin) manufactured by Mitsubishi ケミカル; "jER 1010" (bisphenol a type epoxy resin) manufactured by mitsubishi ケミカル; "jER 1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi ケミカル; "WHR 991S" (phenol-phthalimidine type epoxy resin) manufactured by Nippon chemical Co., Ltd. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
The liquid epoxy resin (a-2) is preferably a liquid epoxy resin having 2 or more epoxy groups in 1 molecule.
The (a-2) liquid epoxy resin is preferably a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, a hydrogenated bisphenol a type epoxy resin, a naphthalene type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a phenol novolac type epoxy resin, an alicyclic epoxy resin having an ester skeleton, a cyclohexane type epoxy resin, a cyclohexane dimethanol type epoxy resin, or an epoxy resin having a butadiene structure.
Specific examples of the liquid epoxy resin (A-2) include "HP 4032", "HP 4032D" and "HP 4032 SS" (naphthalene type epoxy resin) manufactured by DIC; "828 US", "828 EL", "jER 828 EL", "825", "エピコート 828 EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi ケミカル; "jER 807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi ケミカル; "jER 152" (phenol novolac type epoxy resin) manufactured by mitsubishi ケミカル corporation; "630", "630 LSD" and "604" (glycidyl amine type epoxy resins) manufactured by Mitsubishi ケミカル Co., Ltd.; "ED-523T" (a glycyrrhizin-type epoxy resin) manufactured by ADEKA corporation; "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) manufactured by ADEKA; EP-4088S (dicyclopentadiene type epoxy resin) manufactured by ADEKA Co; "ZX 1059" (a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon iron ケミカル & マテリアル; "EX-721" (glycidyl ester type epoxy resin) manufactured by ナガセケムテックス Co; "セロキサイド 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by ダイセル; ダイセル, "PB-3600", JP-100 "and" JP-200 "each of Japan Caoda (epoxy resins having a butadiene structure); "ZX 1658" and "ZX 1658 GS" (1, 4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon iron ケミカル & マテリアル, and "YX 8000" (hydrogenated bisphenol A-type epoxy resin) manufactured by Mitsubishi ケミカル. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
(A) The epoxy resin may be any of (a-1) a solid epoxy resin, (a-2) a liquid epoxy resin, or a combination thereof, and preferably includes (a-1) a solid epoxy resin, and particularly preferably includes a combination of (a-1) a solid epoxy resin and (a-2) a liquid epoxy resin.
When the epoxy resin (A) is used in combination with the solid epoxy resin (A-1) and the liquid epoxy resin (A-2), the mass ratio of the solid epoxy resin (A-1) to the liquid epoxy resin (A-2) is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, and particularly preferably 3:1 to 1: 3.
(A) The epoxy equivalent of the epoxy resin is preferably 50g/eq to 5,000g/eq, more preferably 60g/eq to 1,000g/eq, further preferably 80g/eq to 500g/eq, and further preferably 100g/eq to 300g/eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured according to JIS K7236.
(A) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and further preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (a) epoxy resin is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and particularly preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
The content of the (a-1) solid epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 17% by mass or less, and particularly preferably 15% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
The content of the (a-2) liquid epoxy resin is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 7% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 17% by mass or less, and particularly preferably 15% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
< B) white inorganic pigment >
The resin composition of the present invention contains (B) a white inorganic pigment. In one embodiment, the white inorganic pigment (B) is an inorganic compound having a reflectance of 90% or more with respect to light having a wavelength of 500 nm. (B) The white inorganic pigment does not include silica. (B) The white inorganic pigment has a function of improving the reflectance. (B) The white inorganic pigments may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the material of the white inorganic pigment (B) include white metal oxides such as aluminum oxide (ALUMINA), titanium oxide, zirconium oxide, magnesium oxide, zinc oxide, cerium oxide, antimony oxide, tin oxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, barium zirconate, and calcium zirconate; white metal sulfides such as zinc sulfide and strontium sulfide; white metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; white metal nitrides such as boron nitride, aluminum nitride, and manganese nitride; white metal carbonates such as calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, and lead carbonate; white metal sulfates such as barium sulfate, calcium sulfate, and lead sulfate; white metal phosphates such as zinc phosphate, titanium phosphate, zirconium phosphate, and zirconium phosphotungstate; white metal borates such as aluminum borate; white minerals such as cordierite, talc, clay, mica, hydrotalcite, and boehmite, and among these, alumina, titania, zirconia, magnesia, barium titanate, zinc oxide, ceria, and calcium carbonate are preferable, and titania is particularly preferable. As the titanium oxide, any of rutile type, anatase type, and brookite type can be used, and among them, rutile type is preferable from the viewpoint of further improving the reflectance and the reflectance after the heat resistance test. Titanium oxide obtained by a method such as a sulfuric acid method or a chlorine method can be used. (B) The white inorganic pigment may be 1 kind of the single material or a mixture of two or more kinds of the materials. (B) The shape of the white inorganic pigment may be, for example, any of an irregular shape, a crushed shape, a flake shape, or a spherical shape.
Examples of commercially available white inorganic pigments (B) include "PX 3788" made by sakai chemical industry corporation; タイペーク "CR-50", "CR-57", "CR-80", "CR-90", "CR-93", "CR-95", "CR-97", "CR-60", "CR-63", "CR-67", "CR-58", "CR-85", "UT 771", manufactured by Stone Productivity Ltd; デュポン, タイピュア "R-100", "R-101", "R-102", "R-103", "R-104", "R-105", "R-108", "R-900", "R-902", "R-960", "R-706", "R-931"; "AHP 300" manufactured by light metals of Japan; アルナビーズ "CB-P05" and "CB-A30S" manufactured by Showa electrician.
The specific surface area of the white inorganic pigment (B) is preferably 0.5m2A value of 1m or more, more preferably 1 g or more2A specific ratio of 2m or more/g2More than g. The upper limit is not particularly limited, but is preferably 80m270m below/g2Less than g or 60m2The ratio of the carbon atoms to the carbon atoms is less than g. The specific surface area can be obtained as follows: according to the BET method, nitrogen gas was adsorbed to the surface of the sample using a specific surface area measuring apparatus (Macsorb HM-1210, manufactured by マウンテック Co., Ltd.), and the specific surface area was calculated using the BET multipoint method.
From the viewpoint of remarkably obtaining the desired effect of the present invention, the average particle diameter of the (B) white inorganic pigment is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more, and is preferably 5 μm or less, more preferably 2 μm or less, and further preferably 1 μm or less.
(B) The average particle diameter of the white inorganic pigment can be determined by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the white inorganic pigment (B) can be prepared on a volume basis by using a laser diffraction scattering particle size distribution measuring apparatus, and the median particle size can be measured as an average particle size. The measurement sample used was a sample obtained by weighing 100mg of the white inorganic pigment (B) and 10g of methyl ethyl ketone in a vial and dispersing them for 10 minutes by ultrasonic waves. The volume-based particle size distribution of the white inorganic pigment (B) was measured by a flow cell method using a laser diffraction type particle size distribution measuring apparatus with the wavelengths of the light source used being blue and red, and the average particle size was calculated as the median particle size from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring apparatus include "LA-960" manufactured by horiba, Inc.
From the viewpoint of improving moisture resistance and dispersibility, the (B) white inorganic pigment is preferably treated with a surface treatment agent. The surface treatment agent may be used alone in 1 kind, or may be used in combination of two or more kinds. Examples of the surface treatment agent include silane coupling agents such as a vinyl silane coupling agent, an epoxy silane coupling agent, a styrene silane coupling agent, (meth) acrylic silane coupling agent, an amino silane coupling agent, an isocyanurate silane coupling agent, a ureide silane coupling agent, a mercapto silane coupling agent, an isocyanate silane coupling agent, an acid anhydride silane coupling agent, an alkyl silane coupling agent, and a phenyl silane coupling agent. The surface treatment agent is preferably a silane coupling agent containing no nitrogen atom, and particularly preferably a silane coupling agent selected from the group consisting of a phenyl silane coupling agent, an alkyl silane coupling agent, an epoxy silane coupling agent, a vinyl silane coupling agent, (meth) acrylic silane coupling agent, and a styrene silane coupling agent, from the viewpoints of improving reflectance, suppressing yellowing, and reducing adhesion of copper.
Examples of the phenylsilane coupling agent include phenyltrimethoxysilane and phenyltriethoxysilane. Examples of the alkylsilane coupling agent include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilyl) hexane, and the like. Examples of the epoxy silane coupling agent include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane.
Examples of the vinyl silane coupling agent include vinyltrimethoxysilane and vinyltriethoxysilane. Examples of the (meth) acrylic silane coupling agent include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. Examples of the styrene-based silane coupling agent include p-styryltrimethoxysilane.
Examples of commercially available surface treatment agents include "KBM-103" and "KBE-103" (phenylsilane coupling agents) manufactured by shin-Etsu chemical industries, Ltd.; "KBM-13", "KBM-22", "KBE-13", "KBE-22", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (alkylsilane coupling agent); "KBM-1003" and "KBE-1003" (vinyl silane coupling agent); "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503", "KBM-5103" ((meth) acrylic silane coupling agent), and the like.
From the viewpoint of improving the dispersibility of the white inorganic pigment (B), the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, (B) 100 parts by mass of the white inorganic pigment is preferably surface-treated with 0.2 to 5 parts by mass of a surface treatment agent, more preferably 0.2 to 3 parts by mass, and most preferably 0.3 to 2 parts by mass.
Process for surface treatment with surface treating agentThe degree can be evaluated by the amount of carbon per unit surface area of the (B) white inorganic pigment. From the viewpoint of improving the dispersibility of the (B) white inorganic pigment, the carbon amount per unit surface area of the (B) white inorganic pigment is preferably 0.02mg/m2Above, more preferably 0.1mg/m2Above, more preferably 0.2mg/m2The above. On the other hand, from the viewpoint of suppressing the increase in melt viscosity of the resin composition and the melt viscosity in the sheet state, it is preferably 1mg/m2Less than, more preferably 0.8mg/m2The concentration is preferably 0.5mg/m or less2The following.
(B) The amount of carbon per unit surface area of the white inorganic pigment can be measured by washing the surface-treated (B) white inorganic pigment with a solvent (e.g., Methyl Ethyl Ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the (B) white inorganic pigment surface-treated with the surface treatment agent, and ultrasonic cleaning was performed at 25 ℃ for 5 minutes. After removing the supernatant liquid and drying the solid component, the carbon amount per unit surface area of the (B) white inorganic pigment can be determined using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by horiba, etc. can be used.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (B) white inorganic pigment is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
< (C) silica >
The resin composition of the present invention contains (C) silica.
Examples of the silica (C) include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. The silica (C) is preferably spherical silica. (C) The specific surface area and the average particle diameter of silica are the same as those of (B) the white inorganic pigment. (C) The silica may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Commercially available products of silica (C) include, for example, "UFP-30" manufactured by デンカ; "SP 60-05" and "SP 507-05" manufactured by Nippon iron ケミカル & マテリアル; "YC 100C", "YA 050C", "YA 050C-MJE", "YA 010C" manufactured by アドマテックス; トクヤマ, "シルフィル NSS-3N", "シルフィル NSS-4N" and "シルフィル NSS-5N"; アドマテックス, "SC 2500 SQ", "SO-C4", "SO-C2", and "SO-C1".
From the viewpoint of improving moisture resistance and dispersibility, the (C) silica is preferably treated with a surface treatment agent. Examples of the surface-treating agent include those similar to the surface-treating agent for the white inorganic pigment (B). (C) The degree of surface treatment of silica with the surface treatment agent is the same as that of the white inorganic pigment (B).
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (C) silica is preferably 70% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, particularly preferably 35% by mass or less, and is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, particularly preferably 15% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
The total content of the white inorganic pigment (B) and the silica (C) is 70% by mass or less, preferably 68% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass. In addition, the total content of the (B) white inorganic pigment and the (C) silica is preferably 20 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, and particularly preferably 50 mass% or more, when the nonvolatile content in the resin composition is 100 mass%, from the viewpoint of suppressing cracks while maintaining high reflectance.
From the viewpoint of suppressing cracking while maintaining high reflectance, the mass ratio of (C) silica to (B) white inorganic pigment ((mass of component (C)/(mass of component (B)) is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.5 or more, and particularly preferably 0.8 or more, and is preferably 20.0 or less, more preferably 10.0 or less, further preferably 5.0 or less, and particularly preferably 2.0 or less.
(A) The mass ratio of the epoxy resin to the total of (B) the white inorganic pigment and (C) the silica ((mass of component (a)/(mass of components (B) and (C)) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and particularly preferably 0.2 or more, and is preferably 5.0 or less, more preferably 2.0 or less, further preferably 1.0 or less, and particularly preferably 0.5 or less.
< thermoplastic resin (D) >
The resin composition of the present invention may contain (D) a thermoplastic resin as an optional component. (D) The thermoplastic resin may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
Examples of the thermoplastic resin (D) include phenoxy resins, polyvinyl acetal resins, acrylic resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polyetherimide resins, polycarbonate resins, polyetheretherketone resins, and polyester resins, and among them, preferred are resins selected from phenoxy resins, acrylic resins, and polyphenylene ether resins.
Examples of the phenoxy resin include phenoxy resins having 1 or more kinds of skeletons selected from a bisphenol a skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The end of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone in 1 kind, or in combination with 2 or more kinds. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins having a bisphenol a skeleton) manufactured by mitsubishi ケミカル, "YX 8100" (phenoxy resin having a bisphenol S skeleton) and "YX 6954" (phenoxy resin having a bisphenol acetophenone skeleton), "FX 280" and "FX 293" manufactured by mitsubishi ケミカル & マテリアル, "YX 7200B 35", "YL 7500BH 30", "YX 6954BH 30", "YX 7553BH 30", "YL 7769BH 30", "YL 6794", "YL 7213", "YL 7290" and "YL 7482" manufactured by mitsubishi ケミカル.
Examples of the polyvinyl acetal resin include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "electrochemical ブチラール 4000-2", "electrochemical ブチラール 5000-A", "electrochemical ブチラール 6000-C", "electrochemical ブチラール 6000-EP" manufactured by electrochemical industries, エスレック BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by hydrochemical industries.
The acrylic resin is a polymer obtained by polymerizing a monomer component including a (meth) acrylate monomer. The monomer component constituting the acrylic resin may contain, as a copolymerization component, a (meth) acrylamide monomer, a styrene monomer, a functional group-containing monomer, and the like in addition to the (meth) acrylate monomer. Specific examples of the acrylic resin include "ARUFON UP-1000", "ARUFON UP-1010", "ARUFON UP-1020", "ARUFON UP-1021", "ARUFON UP-1061", "ARUFON UP-1080", "ARUFON UP-1110", "ARUFON UP-1170", "ARUFON UP-1190", "ARUFON UP-1500", "ARUFON UH-2000", "ARUFON-2041", "ARUFON UH-2190", "ARUFON UHE-2012", "ARUFON UC-3510", "ARUFON UG 401-0", "ARUFON US-6100" and ARUFON US-6170 "manufactured by Tokya. These can be used alone in 1 kind, also can be combined with more than 2 kinds.
Examples of the polyolefin resin include ethylene copolymer resins such as low density polyethylene, ultra-low density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; polyolefin elastomers such as polypropylene and ethylene-propylene block copolymers.
Examples of the polybutadiene resin include resins having a hydrogenated polybutadiene skeleton, polybutadiene resins having hydroxyl groups, polybutadiene resins having phenolic hydroxyl groups, polybutadiene resins having carboxyl groups, polybutadiene resins having acid anhydride groups, polybutadiene resins having epoxy groups, polybutadiene resins having isocyanate groups, polybutadiene resins having urethane groups, and polyphenylene ether-polybutadiene resins.
Specific examples of the polyimide resin include "リカコート SN 20" and "リカコート PN 20" manufactured by New Japan chemical and chemical Co. Specific examples of the polyimide resin include linear polyimides obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimides described in jp 2006-37083 a); modified polyimides such as polyimides containing a polysiloxane skeleton (described in Japanese patent laid-open Nos. 2002-12667 and 2000-319386).
Specific examples of the polyamideimide resin include "バイロマックス HR11 NN" and "バイロマックス HR16 NN" manufactured by toyobo seika corporation. Specific examples of the polyamide-imide resin include modified polyamide-imides such as "KS 9100" and "KS 9300" (polyamide-imide having a polysiloxane skeleton) manufactured by hitachi chemical industry.
Specific examples of the polyether sulfone resin include "PES 5003P" manufactured by sumitomo chemical corporation.
Specific examples of polysulfone resins include polysulfone "P1700" and polysulfone "P3500" manufactured by ソルベイアドバンストポリマーズ.
Specific examples of the polyphenylene ether resin include an oligophenylene ether-styrene resin "OPE-2 St 1200" or "OPE-2 St 2200" manufactured by Mitsubishi gas chemical corporation, and "NORYL SA 90" manufactured by SABIC corporation. Specific examples of the polyetherimide resin include "ウルテム" manufactured by GE corporation.
Examples of the polycarbonate resin include a hydroxyl group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxyl group-containing carbonate resin, an anhydride group-containing carbonate resin, an isocyanate group-containing carbonate resin, and a carbamate group-containing carbonate resin. Specific examples of the polycarbonate resin include "FPC 0220" manufactured by Mitsubishi gas chemical company, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei ケミカル ズ company, "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by クラレ company. Specific examples of the polyether ether ketone resin include "スミプロイ K" manufactured by Sumitomo chemical Co. Examples of the polyester resin include polyethylene terephthalate resins.
(D) The weight average molecular weight of the thermoplastic resin is preferably 81,000 or more, more preferably 5,000 or more, further preferably 10,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, further preferably 60,000 or less. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by a Gel Permeation Chromatography (GPC) method.
(D) The thermoplastic resin preferably has a transmittance of 80% or more for light having a wavelength of 450nm incident on the film surface when the film is formed into a film of 20 μm in the vertical direction.
The content of the (D) thermoplastic resin is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less, for example, 0% by mass or more, 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 10% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
< curing agent (E) >
The resin composition of the present invention may contain (E) a curing agent as an optional component. (E) The curing agent has a function of curing the resin composition by reacting with the epoxy resin (a). (E) The curing agent may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The curing agent (E) is not particularly limited, and examples thereof include a phenol curing agent, a carbodiimide curing agent, an acid anhydride curing agent, an amine curing agent, a benzoxazine curing agent, a cyanate curing agent, and a thiol curing agent. (E) The curing agent preferably comprises a phenolic curing agent.
The phenol curing agent is a curing agent having 2 or more phenolic hydroxyl groups in 1 molecule, and examples thereof include a bisphenol curing agent, a biphenyl type phenol curing agent, a naphthalene type phenol curing agent, a phenol novolac type phenol curing agent, a naphthalene ether type phenol curing agent, a phenol curing agent containing a triazine skeleton, a polyphenylene ether type phenol curing agent, a phenol aralkyl type phenol curing agent, a cresol novolac type phenol curing agent, and a bisphenol type phenol curing agent, among which a bisphenol curing agent is preferable, a bisphenol curing agent selected from a bisphenol compound having a fluorine atom, a bisphenol compound having an alicyclic structure, and a bisphenol compound having a fluorene skeleton is more preferable, a bisphenol compound having a fluorine atom is further preferable, and bisphenol AF is particularly preferable.
As commercially available products of the phenolic curing agent (B-1), specifically, "BIS-AF" and "BIS-Z" manufactured by セントラル Nitrosum corporation are mentioned; "BisOFP-A", "BisOC-FL", "BisP-CDE", etc., of the State chemical industries, Inc.
The carbodiimide-based curing agent is a curing agent having 2 or more carbodiimide structures in 1 molecule, and examples thereof include aliphatic bis-carbodiimides such as tetramethylene-bis (t-butylcarbodiimide) and cyclohexane-bis (methylene-t-butylcarbodiimide); a bis-carbodiimide such as an aromatic bis-carbodiimide such as phenylene-bis (xylylcarbodiimide); aliphatic polycarbodiimides such as polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, polycyclohexylene carbodiimide, poly (methylenedicyclohexylcarbodiimide), and poly (isophorone carbodiimide); polycarbodiimides such as aromatic polycarbodiimides including poly (phenylene carbodiimide), poly (naphthylene carbodiimide), poly (toluene carbodiimide), poly (methyldiisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), poly (diethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide), poly (diisopropylphenylene carbodiimide), poly (xylylene carbodiimide), poly (tetramethylxylylene carbodiimide), poly (methylenediphenylene carbodiimide), and poly [ methylenebis (methylphenylene) carbodiimide ].
Commercially available carbodiimide-based curing agents include, for example, "カルボジライト V-02B", "カルボジライト V-03", "カルボジライト V-04K", "カルボジライト V-07" and "カルボジライト V-09" manufactured by Nisshinbo ケミカル; ラインケミー, "スタバクゾール P", "スタバクゾール P400" and "ハイカジル 510".
The acid anhydride curing agent is a curing agent having 1 or more carboxylic anhydride groups (-CO-O-CO-) in 1 molecule, and examples thereof include aromatic acid anhydride curing agents such as phthalic anhydride, pyromellitic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3 ', 4,4 ' -diphenylsulfone tetracarboxylic dianhydride, 3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride, 3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride, and methylene-4, 4 ' -biphthalic dianhydride; aliphatic acid anhydride-based curing agents such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, cyclopentanetetracarboxylic dianhydride, and cyclohexane-1, 2,4, 5-tetracarboxylic dianhydride; and polymer anhydride-based curing agents such as styrene/maleic anhydride copolymers and alkyl (meth) acrylate/styrene/maleic anhydride copolymers. Examples of commercially available acid anhydride curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA", and "YH-306", "YH-307" manufactured by Mitsubishi ケミカル, and "HN-2200" and "HN-5500" manufactured by Hitachi chemical Co., Ltd.
The amine-based curing agent is a curing agent having 2 or more amino groups, and examples thereof include aliphatic amines, polyether amines, alicyclic amines, aromatic amines, and the like, and among them, aromatic amines are preferable from the viewpoint of exhibiting the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine-based curing agent include 4,4 '-methylenebis (2, 6-dimethylaniline), 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4 '-diaminodiphenyl ether, 3' -dimethyl-4, 4 '-diaminobiphenyl, 2' -dimethyl-4, 4 '-diaminobiphenyl, 3' -dihydroxybenzidine, 2-bis (3-amino-4-hydroxyphenyl) propane, 3-dimethyl-5, 5-diethyl-4, 4-diphenylmethanediamine, 2-bis (4-aminophenyl) propane, and the like, 2, 2-bis (4- (4-aminophenoxy) phenyl) propane, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone and the like. As the amine-based curing agent, commercially available ones can be used, and examples thereof include "SEIKACURE-S" manufactured by セイカ, and "KAYABOND C-200S", "KAYABOND C-100", "カヤハード A-A", "カヤハード A-B", "カヤハード A-S", and "エピキュア W" manufactured by Mitsubishi ケミカル, and the like.
Specific examples of the benzoxazine-based curing agent include "JBZ-OP 100D" and "ODA-BOZ" manufactured by JFE ケミカル; "HFB 2006M" available from Showa Polymer Co; "P-d" and "F-a" manufactured by four national chemical industries, Inc.
Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenolic cyanate (oligo (3-methylene-1, 5-phenylene cyanate)), 4 '-methylenebis (2, 6-dimethylphenylcyanate), 4' -ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, difunctional cyanate ester resins such as 2, 2-bis (4-cyanate) phenylpropane, 1-bis (4-cyanatophenylmethane), bis (4-cyanate-3, 5-dimethylphenyl) methane, 1, 3-bis (4-cyanatophenyl-1- (methylethylidene)) benzene, bis (4-cyanatophenyl) sulfide, and bis (4-cyanatophenyl) ether; polyfunctional cyanate ester resins derived from phenol novolak, cresol novolak and the like; prepolymers obtained by partially triazinating these cyanate ester resins, and the like. Specific examples of the cyanate-based curing agent include "PT 30" and "PT 60" (both of which are phenol novolac type polyfunctional cyanate ester resins) manufactured by ロンザジャパン, and "BA 230" and "BA 230S 75" (prepolymers in which a part or all of bisphenol a dicyanate ester is triazinized to form a trimer).
The thiol curing agent is a curing agent having 2 or more mercapto groups, and examples thereof include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tris (3-mercaptopropyl) isocyanurate, and the like.
(E) The equivalent weight of the reactive group of the curing agent is preferably 50g/eq to 3000g/eq, more preferably 100g/eq to 1000g/eq, further preferably 100g/eq to 500g/eq, and particularly preferably 100g/eq to 300g/eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of the reactive group. The reactive group is, for example, a phenolic hydroxyl group when it is a phenolic curing agent. In the case of an acid anhydride-based curing agent, 1 equivalent of a carboxylic anhydride group (-CO-O-CO-) corresponds to 2 equivalents of the reactive group.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (E) curing agent is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, for example, 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, and particularly preferably 3% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
< curing accelerators (F) >
The resin composition of the present invention may contain (F) a curing accelerator as an optional component. (F) The curing accelerator has a function of accelerating the curing reaction of the epoxy resin (a). (F) The curing accelerator may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
Examples of the curing accelerator (F) include phosphorus-based curing accelerators, imidazole-based curing accelerators, amine-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Among these, the (F) curing accelerator is preferably a phosphorus-based curing accelerator or an imidazole-based curing accelerator, and more preferably a phosphorus-based curing accelerator, from the viewpoint of achieving a higher reflectance.
The phosphorus-based curing accelerator preferably contains 1 or more selected from among phosphonium salts and phosphines from the viewpoint of achieving higher reflectance.
Examples of the phosphonium salt include aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis (tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hexahydrophthalate, tetrabutylphosphonium-2, 6-bis [ (2-hydroxy-5-methylphenyl) methyl ] -4-methylphenoxide, di-t-butylmethylphosphonium tetraphenylborate and the like; onium salts such as methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyl triphenyl 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, butyl triphenyl phosphonium thiocyanate and the like.
Examples of the phosphine include aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, and tricyclohexylphosphine; dibutylphenylphosphine, di-t-butylphenyl phosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri (4-ethylphenyl) phosphine, tri (4-propylphenyl) phosphine, tri (4-isopropylphenyl) phosphine, tri (4-butylphenyl) phosphine, tri (4-t-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, triphenylphosphine, tri (4-t-butylphenyl) phosphine, tri (4-methylphenyl) phosphine, tri (4-methoxyphenyl) phosphine, tri (4-methylphenyl) phosphine, tri (4-phenyl) phosphine, tri (4-methylphenyl) phosphine, tri (4-butyl-phenyl) phosphine, tri (4-phenyl) phosphine, tri (2-phenyl) phosphine, tri (4, tri (2-phenyl) phosphine, tri (4, tri (2-butyl-phenyl) phosphine, tri (2-butyl, tri (4, tri (2-phenyl) phosphine, tri (4, tri-phenyl) phosphine, tri (2-butyl, tri (4, tri-phenyl) phosphine, tri (2-phenyl) phosphine, tri (, Aromatic phosphines such as tris (4-methoxyphenyl) phosphine, tris (4-ethoxyphenyl) phosphine, tris (4-tert-butoxyphenyl) phosphine, diphenyl-2-pyridylphosphine, 1, 2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1, 4-bis (diphenylphosphino) butane, 1, 2-bis (diphenylphosphino) acetylene, and 2, 2' -bis (diphenylphosphino) diphenyl ether; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; and aromatic phosphine-quinone addition reaction products such as triphenylphosphine-p-benzoquinone addition reaction products.
As the phosphorus-based curing accelerator, commercially available products such as "TBP-DA" manufactured by Beixing chemical industry Co., Ltd. can be used.
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, 2-heptadecylimidazole, 1, 2-dimethylimidazole, 2-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-cyanoethyl-2-methylimidazole, 2-decylimidazole, 2-ethylimidazole, 2-decylimidazole, 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-decylimidazole, and mixtures thereof, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -undecylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -ethyl-4 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine, 2, 4-diamino-6- [2 ' -methylimidazolyl- (1 ') ] -ethyl-s-triazine isocyanuric acid adduct, and mixtures thereof, Imidazole compounds such as 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2, 3-dihydro-1H-pyrrolo [1,2-a ] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.
As the imidazole-based curing accelerator, commercially available products such as "P200-H50" manufactured by Mitsubishi ケミカル company and "1B 2 PZ-10M" manufactured by four nationwide chemical companies can be used.
Examples of the amine-based 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, preferably 4-dimethylaminopyridine, 1, 8-diazabicyclo (5,4,0) -undecene.
Examples of the guanidine-based 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, dicyandiamide, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene are preferred.
Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organic metal 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 (II) acetylacetonate; organic iron complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
From the viewpoint of remarkably obtaining the effect of the present invention, the content of the (F) curing accelerator is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.8% by mass or less, for example, 0% by mass or more, 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more, with respect to 100% by mass of nonvolatile components in the resin composition.
< G other additives >
The resin composition of the present invention may contain an optional additive as a nonvolatile component. Examples of such additives include organic fillers such as rubber particles; leveling agents such as silicone leveling agents and acrylic polymer leveling agents; thickeners such as bentonite and montmorillonite; defoaming agents such as silicone defoaming agents, acrylic defoaming agents, fluorine defoaming agents, and vinyl resin defoaming agents; ultraviolet absorbers such as benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers and salicylic acid-based ultraviolet absorbers; adhesion improvers 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; 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 ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen flame retardants (e.g., melamine sulfate), halogen flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate dispersants, polyoxyalkylene dispersants, acetylene dispersants, silicone dispersants, anionic dispersants, and cationic dispersants; and stabilizers such as borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers, and carboxylic acid anhydride stabilizers. (G) The other additives may be used alone in an amount of 1, or in combination in an amount of 2 or more in any ratio. The content of (G) other additives can be appropriately set if it is a person skilled in the art.
(H) organic solvent
The resin composition of the present invention may contain an optional organic solvent as a volatile component in addition to the nonvolatile component. As the organic solvent (H), known solvents can be suitably used, and the kind thereof is not particularly limited. Examples of the organic solvent (H) include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ -butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1, 4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, 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, diethylene glycol ethyl acetate, γ -butyrolactone, and methyl methoxypropionate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and 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; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (H) The organic solvent may be used alone in 1 kind, or may be used in combination in 2 or more kinds at an arbitrary ratio.
(H) The content of the 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, 5 mass% or less, or the like, when the total content in the resin composition is 100 mass%.
The method for producing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the above-described components are added to an arbitrary container and mixed/dispersed using a rotary stirrer or the like.
< Properties and applications of resin composition >
According to the resin composition of the present invention, a cured product having excellent reflectance can be obtained. Therefore, the resin composition of the present invention can be suitably used as a resin composition (light-reflecting resin composition) used for obtaining a cured product for light-reflecting use for reflecting light from a light source. Specifically, the resin composition can be suitably used for a reflective sheet formed on the outermost layer of a printed wiring board. Examples of the light source include a Light Emitting Diode (LED), a small LED, and a micro LED. Further, the resin composition of the present invention can also be suitably used as a resin composition for insulation of a solder resist layer of a printed wiring board. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming a layer having both a solder resist layer and a reflective sheet. Further, the resin composition of the present invention can be suitably used as a resin composition for interlayer insulation of a printed wiring board. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming an interlayer insulating layer.
The resin composition of the present invention contains (A) an epoxy resin, (B) a white inorganic pigment, and (C) silica, and the total content of the (B) white inorganic pigment and the (C) silica is 70% by mass or less. By using such a resin composition, a cured product can be obtained in which the occurrence of cracks can be suppressed while maintaining a high reflectance. In one embodiment, by using such a resin composition, a cured product with a low relative dielectric constant (Dk) can be obtained. In one embodiment, a cured product having excellent tensile properties can be obtained by using such a resin composition.
The cured product of the resin composition of the present invention can have a high reflectance. Therefore, in one embodiment, the reflectance of a cured product of the resin composition (cured product obtained by heating at 180 ℃ for 60 minutes) with respect to light having a wavelength of 460nm is preferably 80% or more, more preferably 85% or more, further preferably 90% or more, and particularly preferably 95% or more, as measured in the following test example 3.
The cured product of the resin composition of the present invention can have a feature of being capable of suppressing the occurrence of cracks. Therefore, in one embodiment, when the crack resistance is tested as in test example 2 described below, it is preferable that the number of cracks is less than 3, and it is particularly preferable that the number of cracks is 0.
In one embodiment, a cured product of the resin composition of the present invention can have a low relative dielectric constant (Dk). Therefore, in one embodiment, the relative dielectric constant (Dk) of a cured product of the resin composition (a cured product obtained by heating at 200 ℃ for 90 minutes) when measured at 5.8GHz and 23 ℃ as in test example 4 described below is preferably 8.0 or less, more preferably 7.0 or less, further preferably 6.0 or less, still further preferably 5.5 or less, and particularly preferably 5.0 or less.
In one embodiment, the cured product of the resin composition of the present invention has excellent tensile properties. Therefore, in one embodiment, the elongation of the cured product of the resin composition (cured product obtained by heating at 180 ℃ for 90 minutes) measured at 25 ℃ in accordance with JIS K7161 as in test example 1 described below is preferably 2% or more, more preferably 3% or more, and still more preferably 4% or more.
[ resin sheet ]
The resin sheet of the present invention includes a support and a resin composition layer provided on the support and formed of the resin composition of the present invention.
The thickness of the resin composition layer is preferably 200 μm or less, more preferably 100 μm or less, and even more preferably 80 μm or less, from the viewpoint of reducing the thickness of the printed wiring board and providing a cured product having excellent insulation properties even when the cured product of the resin composition is a thin 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 preferably a film made of a plastic material and a metal foil.
When a film made of a plastic material is used as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter, sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter, sometimes abbreviated as "PEN"); acrylic acids such as polycarbonate (hereinafter sometimes abbreviated as "PC") and polymethyl methacrylate (PMMA); cyclic polyolefin, cellulose Triacetate (TAC), polyether sulfide (PES), polyether ketone, polyimide, and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and particularly, inexpensive polyethylene terephthalate is preferable.
When a metal foil is used as the support, examples of the metal foil include a copper foil and an aluminum foil, and a copper foil is preferable. As the copper foil, a foil formed of a simple metal of copper may be used, and a foil formed of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, or the like) may also be used.
The surface of the support to be bonded to the resin composition layer may be subjected to matting treatment, corona treatment, or antistatic treatment.
As the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. Examples of the release agent used for the release layer of the support with a release layer include 1 or more release agents selected from alkyd resins, polyolefin resins, urethane resins, and silicone resins. As the support with a release layer, commercially available products can be used, and examples thereof include PET films having a release layer containing an alkyd resin-based release agent as a main component, "PET 501010", "SK-1", "AL-5", "AL-7", manufactured by リンテック; "Lumiror T60" manufactured by east レ Co., Ltd.; "ピューレックス" by Imperial corporation; ユニチカ, "ユニピール" manufactured by the same company.
The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.
In one embodiment, the resin sheet may further comprise other layers as desired. Examples of the other layer include a protective film provided on a surface of the resin composition layer not bonded to the support (i.e., a surface opposite to the support) and formed by 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, adhesion of dirt or the like on the surface of the resin composition layer and scratches can be suppressed.
The resin sheet can be produced as follows: for example, a liquid resin composition is used as it is or a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, and the resin composition is applied to a support using a die coater or the like and dried to form a resin composition layer.
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 in 1 kind, or may be used in combination in 2 or more kinds.
The drying can be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, and the resin composition layer is dried so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. Although the boiling point of the organic solvent in the resin composition (resin varnish) varies, when a resin composition (resin varnish) containing 30 to 60 mass% of the organic solvent is used, for example, the resin composition layer can be formed by drying at 50 to 150 ℃ for 3 to 10 minutes.
The resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, the protective film may be peeled off for use.
The resin composition of the present invention used in the resin composition layer has a low melt viscosity and therefore has excellent flexibility. Therefore, the resin sheet exhibits excellent flexibility. Specifically, when the resin sheet is bent at 180 ℃ along an axis having a diameter of 1mm so that the support body is located inside, cracking of the resin sheet is suppressed.
[ cured product ]
The cured product of the present invention can be obtained by curing the resin composition of the present invention. The curing conditions for the resin composition may be those in the step (II) described below. Further, the preheating may be performed before the resin composition is cured, and the heating including the preheating may be performed a plurality of times.
[ reflecting sheet, printed Circuit Board ]
The reflector of the present invention comprises a cured product of the resin composition of the present invention. Further, the printed circuit board of the present invention comprises the reflective sheet of the present invention. Further, the printed circuit board of the present invention preferably includes a reflective sheet in the form of an interlayer insulating layer or a solder resist layer.
As shown in fig. 1, the printed circuit board 1 has a reflection sheet 3 formed on a substrate 2, and a light source 4 such as a Light Emitting Diode (LED) is disposed on a surface 31 of the reflection sheet 3.
The reflective sheet is a cured product of the resin composition of the present invention, and therefore can reflect light with a high reflectance, and for example, the reflectance of light having a wavelength of 460nm is preferably more than 85%, more preferably 90% or more, and further preferably 92% or more. The upper limit of the reflectance may be set to 100% or less. The reflector also reflects light with a high reflectance even after heat resistance test (temperature 125 ℃ C., 100 hours) treatment because the reflector comprises a cured product of the resin composition of the present invention, and the reflectance of light having a wavelength of 460nm after heat resistance test treatment is preferably more than 80%, more preferably 85% or more, and still more preferably 88% or more, for example. The upper limit of the reflectance after the heat resistance test treatment may be 100% or less. The reflectance and the reflectance after the heat resistance test treatment can be measured by using, for example, a multichannel spectroscope (available from Otsuka electronics Co., Ltd., MCPD-7700).
The printed circuit board and the reflective sheet of the present invention can be produced by a method including the steps (I), (II), and (III) below, using the above resin sheet, for example.
(I) Laminating the resin composition layer of the resin sheet on the substrate so as to be bonded to the substrate;
(II) forming a reflecting sheet by thermally curing the resin composition layer;
(III) disposing a light source on the reflector sheet.
The substrate used in step (I) is not limited, and for example, a circuit board including an insulating layer, a conductor layer formed on the insulating layer, and a solder resist layer formed on the conductor layer can be used.
The lamination of the substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the substrate from the support side. Examples of the member for heat-pressure bonding the resin sheet to the substrate (hereinafter also referred to as "heat-pressure bonded member") include a heated metal plate (such as an SUS cover) and a metal roll (SUS roll). It is preferable that the resin sheet is pressed through an elastic material such as a heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the substrate, instead of directly pressing the heat-pressure bonding member to the resin sheet.
The lamination of the substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably 60-160 ℃, more preferably 80-140 ℃, the heating and crimping pressure is preferably 0.098-1.77 MPa, more preferably 0.29-1.47 MPa, and the heating and crimping time is preferably 20-400 seconds, more preferably 30-300 seconds. The lamination is preferably performed under a reduced pressure of 26.7hPa or less.
The lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Nippon Kasei corporation, vacuum applicators manufactured by ニッコー Seedunculture マテリアル ズ corporation, and batch vacuum pressure laminators.
The smoothing treatment of the laminated resin sheet can be performed by, for example, pressurizing the heat-pressure bonding member from the support side under normal pressure (atmospheric pressure) after the lamination. The pressing conditions for the smoothing treatment may be the same as the above-described conditions for the heat and pressure bonding of the laminate. The smoothing treatment can be performed using a commercially available laminator. The lamination and smoothing processes may be continuously performed using a commercially available vacuum laminator as described above.
The support may be removed between the steps (I) and (II), or may be removed after the step (II).
In the step (II), the resin composition layer is thermally cured to form the reflection sheet. For example, the heat curing conditions of the resin composition layer vary depending on the kind of the resin composition, but the curing temperature is preferably 120 ℃ to 240 ℃, more preferably 130 ℃ to 220 ℃, and still more preferably 150 ℃ to 210 ℃. The curing time is preferably 5 to 120 minutes, more preferably 10 to 100 minutes, and still more preferably 15 to 100 minutes.
Before curing of the resin composition occurs, the resin composition may be preheated at a temperature lower than the curing temperature. For example, before the resin composition is thermally cured, the resin composition may be preheated at a temperature of 50 ℃ or higher and less than 120 ℃ (preferably 60 ℃ or higher and 115 ℃ or lower, more preferably 70 ℃ or higher and 110 ℃ or lower) for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes).
The reflection sheet may have a concave portion in addition to the planar surface as shown in fig. 1 on the light source side in order to improve the extraction efficiency of light emitted from the light source.
In the step (III), the light source is disposed on the reflective sheet. For example, when the surface of the reflection sheet has a concave portion, the light source is disposed in the concave portion.
If necessary, after being electrically connected to the light source, the light source may be fixed by sealing or the like.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following description, "part" and "%" mean "part by mass" and "% by mass", respectively, unless otherwise specified.
< example 1>
4 parts of a liquid bisphenol A type epoxy resin ("jER 828 EL" manufactured by Mitsubishi ケミカル, epoxy equivalent of 180), 4 parts of a solid fluorine atom-containing epoxy resin ("YX 7760" manufactured by Mitsubishi ケミカル, epoxy equivalent of 245g/eq.), and 20 parts of a phenoxy resin having a biphenyl skeleton and a cyclohexane skeleton ("YX 7200B 35" manufactured by Mitsubishi ケミカル, MEK solution having a weight average molecular weight of 30,000, a light transmittance (450nm) of a 20 μm film of 88%, and a solid content of 35% by mass were dissolved in 8 parts of MEK by heating with stirring. Titanium oxide ("PX 3788" manufactured by Sakai chemical industry Co., Ltd., average particle size of 0.26 μm, treated with phenyltrimethoxysilane ("KBM-103" manufactured by shin-Etsu chemical Co., Ltd.), 10 parts of spherical silica ("SO-C2" manufactured by アドマテックス Co., average particle size of 0.5 μm, treated with 3-methacryloxypropyltrimethoxysilane ("KBM-503" manufactured by shin-Etsu chemical Co., Ltd.), 10 parts of bisphenol AF ("BIS-AF" manufactured by セントラル Nitro corporation was adjusted to have a nonvolatile content of 50% with MEK) 4 parts and 0.2 part of a phosphorus-based catalyst ("TBP-DA" manufactured by Beixing chemical industry Co., Ltd.) were mixed and uniformly dispersed with a high-speed rotary stirrer to prepare a resin composition.
< example 2>
A resin composition was prepared in the same manner as in example 1 except that the amount of titanium oxide ("PX 3788" made by Sakai chemical industry Co., Ltd., average particle diameter: 0.26 μm and treated with phenyltrimethoxysilane ("KBM-103" made by shin-Etsu chemical Co., Ltd.) was changed from 10 parts to 14 parts, and the amount of spherical silica ("SO-C2" made by アドマテックス Co., Ltd., average particle diameter: 0.5 μm and treated with 3-methacryloxypropyltrimethoxysilane ("KBM-503" made by shin-Etsu chemical Co., Ltd.) was changed from 10 parts to 6 parts.
< example 3>
A resin composition was prepared in the same manner as in example 1 except that the amount of titanium oxide ("PX 3788" made by Sakai chemical industry Co., Ltd., average particle diameter: 0.26 μm treated with phenyltrimethoxysilane ("KBM-103" made by shin-Etsu chemical Co., Ltd.) was changed from 10 parts to 16 parts, and the amount of spherical silica ("SO-C2" made by アドマテックス Co., average particle diameter: 0.5 μm treated with 3-methacryloxypropyltrimethoxysilane ("KBM-503" made by shin-Etsu chemical Co., Ltd.) was changed from 10 parts to 16 parts.
< example 4>
A resin composition was prepared in the same manner as in example 1 except for using 7 parts of a non-functional acrylic resin ("ARUFON UP-1020" manufactured by tokyo synthesis corporation, having a weight average molecular weight of 2,000 and a light transmittance of a 20 μm film (450nm) of 85%) in place of 20 parts of a phenoxy resin having a biphenyl skeleton and a cyclohexane skeleton ("YX 7200B 35" manufactured by mitsubishi ケミカル corporation, an MEK solution having a weight average molecular weight of 30,000 and a light transmittance of a 20 μm film (450nm) of 88% by mass and a solid content of 35% by mass.
< example 5>
A resin composition was prepared in the same manner as in example 1 except for using 7 parts of a low-molecular-weight polyphenylene ether ("Noryl SA 90" manufactured by Sabic corporation, having a weight-average molecular weight of 1,700 and a light transmittance (450nm) of a 20 μm film of 85%) in place of 20 parts of a phenoxy resin having a biphenyl skeleton and a cyclohexane skeleton ("YX 7200B 35" manufactured by mitsubishi ケミカル corporation, having a weight-average molecular weight of 30,000 and a light transmittance (450nm) of a 20 μm film of 88% by mass and a solid content of 35% by mass.
< example 6>
A resin composition was prepared in the same manner as in example 1 except that 4 parts of a liquid bisphenol a-type epoxy resin ("jER 828 EL" manufactured by mitsubishi ケミカル, epoxy equivalent being 180) and 4 parts of a solid fluorine atom-containing epoxy resin ("YX 7760" manufactured by mitsubishi ケミカル, epoxy equivalent being 245g/eq.) were changed to 4 parts of a hydrogenated liquid epoxy resin ("YX 8000" manufactured by mitsubishi ケミカル, epoxy equivalent being 205g/eq.) and 4 parts of a biphenyl-type epoxy resin ("YX 4000H" manufactured by mitsubishi ケミカル, epoxy equivalent being 195 g/eq.).
< example 7>
A resin composition was prepared in the same manner as in example 1, except that 4 parts of bisphenol AF (a solution prepared by adjusting "BiS-AF" made by セントラル nitre, inc., to a nonvolatile content of 50% with MEK) was not used.
< example 8>
A resin composition was prepared in the same manner as in example 1, except that 0.2 part of a phosphorus-based catalyst ("TBP-DA" manufactured by Beixing chemical industries, Ltd.) was not used.
< comparative example 1>
A resin composition was prepared in the same manner as in example 1 except that the amount of titanium oxide ("PX 3788" made by Sakai chemical industry Co., Ltd., average particle diameter: 0.26 μm and treated with phenyltrimethoxysilane ("KBM-103" made by shin-Etsu chemical Co., Ltd.) was changed from 10 parts to 20 parts, and no spherical silica ("SO-C2" made by アドマテックス Co., average particle diameter: 0.5 μm and treated with 3-methacryloxypropyltrimethoxysilane ("KBM-503" made by shin-Etsu chemical Co., Ltd.) was used in 10 parts.
< comparative example 2>
A resin composition was prepared in the same manner as in example 1 except that the amount of titanium oxide ("PX 3788" made by sakai chemical industry corporation, having an average particle size of 0.26 μm and treated with phenyltrimethoxysilane ("KBM-103" made by shin-Etsu chemical corporation) was changed from 10 parts to 20 parts, the amount of spherical silica ("SO-C2" made by アドマテックス, having an average particle size of 0.5 μm and treated with 3-methacryloxypropyltrimethoxysilane ("KBM-503" made by shin-Etsu chemical corporation) was changed from 10 parts to 20 parts, and the amount of phenoxy resin having a biphenyl skeleton and a cyclohexane skeleton ("YX 7200B 35" made by Mitsubishi ケミカル corporation, having a weight-average molecular weight of 30,000 and a light transmittance (450nm) of a 20 μm film of 88% and a MEK solution having a solid content of 35 mass%) was changed from 20 parts to 15 parts.
< test example 1: measurement of elongation >
As a support, a PET film with a release layer ("PET 501010" manufactured by リンテック Co., Ltd., thickness: 38 μm) was prepared. On the release layer of the support, the resin compositions prepared in examples and comparative examples were uniformly coated so that the thickness of the dried resin composition layer reached 50 μm. Thereafter, the resin composition was heated at 80 ℃ for 4 minutes to prepare a resin sheet including a resin composition layer having a thickness of 50 μm.
The resin sheet was cured at 180 ℃ for 90 minutes. Thereafter, the PET film was peeled off. Tensile tests were carried out using an actinomycete (テンシロン) universal tester (エー, from seeds and seeds アンド, from seeds and seeds デイ) under conditions of a temperature of 25 ℃ (room temperature) and a tensile rate of 50 mm/min in accordance with the japanese industrial standard (JIS K7161), and elongation (%) was measured and evaluated in accordance with the following evaluation criteria.
Evaluation criteria
Very good: elongation of 4% or more
Good: the elongation is more than 3 percent and less than 4 percent
And (delta): the elongation is more than 2 percent and less than 3 percent
X: the elongation is less than 2%.
< test example 2: evaluation of crack resistance >
(1) Production of resin sheet
As a support, a release layer-attached PET film ("AL 5" manufactured by リンテック) was prepared. The resin compositions prepared in examples and comparative examples were uniformly coated on the release layer of the support using a die coater in such a manner that the thickness of the dried resin composition layer reached 100 μm. Thereafter, the mixture was dried at 70 to 120 ℃ (average temperature of 95 ℃) for 7 minutes to prepare a resin sheet.
(2) Manufacture of inner layer circuit substrate
An inner layer circuit board was produced by forming circuit patterns on both surfaces of a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil 18 μm thick, substrate 0.2mm thick, "E679 FGR" manufactured by hitachi corporation) by etching, and roughening treatment with a microetching agent ("CZ 8100" manufactured by メック corporation). A12 mm by 12mm through-hole was formed in the inner layer circuit board by a mechanical drill.
(3) Lamination of temporary resin sheets
A temporary polyimide resin sheet ("PFDKE 1525 PT" manufactured by Kouzo Co., Ltd.) was prepared, and the protective film was peeled off. Thereafter, a temporary resin sheet was laminated on one surface of the inner-layer circuit board so that the adhesive layer was bonded to the inner-layer circuit board using a batch vacuum press laminator (MVLP-500, manufactured by titled machine corporation). The lamination was performed by reducing the pressure for 30 seconds to a pressure of 13hPa or less and then pressing at 100 ℃ and a pressure of 0.74MPa for 30 seconds.
(4) Temporary attachment of dummy wafer and lamination of resin sheet
A 10mm × 10mm dummy wafer was inserted into the hole of the inner layer circuit board with the temporary resin sheet prepared in (3) above. Next, the resin sheet produced in the above (1) was laminated on one surface of the inner-layer circuit board by using a batch vacuum pressure laminator ("MVLP-500" manufactured by titled mechanism corporation) so that the resin composition layer was bonded to the inner-layer circuit board. The lamination was performed by reducing the pressure for 30 seconds to a pressure of 13hPa or less and then pressing at 100 ℃ and a pressure of 0.74MPa for 30 seconds.
(5) Curing of resin composition layer
After the resin sheets were laminated, the resin composition layer was thermally cured at 100 ℃ for 30 minutes and at 170 ℃ for 30 minutes to form an insulating layer. Thereafter, the PET film as the resin sheet support was peeled off.
(6) Stripping of temporary resin sheet and complete curing of insulating layer
After peeling the polyimide-based temporary resin sheet, the insulating layer was completely cured at 200 ℃ for 60 minutes.
(7) Evaluation of crack resistance
A part of the cured product sample obtained in (6) above was cut out, and subjected to heat treatment 20 times using a reflow apparatus ("HAS 6116" manufactured by アントム, having a maximum reaching temperature of 260 ℃). Thereafter, the circuit board with built-in circuit of the pseudo wafer was observed with an optical microscope and evaluated according to the following evaluation criteria.
Evaluation criteria
O: 0 part of crack
And (delta): the number of cracks is more than 1 and less than 3
X: the number of cracks is more than 3.
< test example 3: measurement of reflectance >
The evaluation substrate A obtained in test example 2 was cut into a width of 50mm and a length of 50mm, and the reflectance (%) of light having a wavelength of 460nm was measured by a multi-channel spectroscope (available from Otsuka electronics, MCPD-7700) and evaluated according to the following evaluation standards.
Evaluation criteria
Very good: the reflectivity is more than 95%
Good: the reflectivity is more than 90 percent and less than 95 percent
And (delta): the reflectivity is more than 85 percent and less than 90 percent
X: the reflectivity is less than 85%.
< test example 4: measurement of relative dielectric constant >
The protective film was peeled from the resin sheet obtained in test example 1, and the resin composition layer was thermally cured by heating at 200 ℃ for 90 minutes, and then the support was peeled off to obtain a cured product.
The resulting cured product was cut into test pieces having a width of 2mm and a length of 80 mm. The relative dielectric constant of the test piece was measured by a cavity perturbation method using "HP 8362B" manufactured by アジレントテクノロジーズ company under the conditions of a measurement frequency of 5.8GHz and a measurement temperature of 23 ℃. The measurement was performed on 3 test pieces, and the average value was calculated.
The amounts of nonvolatile components used in the resin compositions of examples and comparative examples, and the measurement results and evaluation results of test examples are shown in table 1 below.
[ Table 1]
Figure 166912DEST_PATH_IMAGE002
From the above results, it can be seen that: by using a resin composition containing (a) an epoxy resin, (B) a white inorganic pigment and (C) silica, and having a total content of the (B) white inorganic pigment and the (C) silica of 70 mass% or less, a cured product capable of suppressing the occurrence of cracks while maintaining a high reflectance can be obtained.
Description of the reference numerals
1 printed circuit board
2 base plate
3 reflective sheet
31 face of reflecting sheet
4 light source

Claims (19)

1. A resin composition comprising (A) an epoxy resin, (B) a white inorganic pigment, and (C) silica,
the total content of the component (B) and the component (C) is 70% by mass or less, assuming that the nonvolatile content in the resin composition is 100% by mass.
2. The resin composition according to claim 1, wherein the component (A) comprises (A-1) an epoxy resin which is solid at a temperature of 25 ℃.
3. The resin composition according to claim 1, wherein the total content of the component (B) and the component (C) is 30% by mass or more, assuming that the nonvolatile content in the resin composition is 100% by mass.
4. The resin composition according to claim 1, wherein the mass ratio of the component (C) to the component (B) (mass of component (C)/mass of component (B)) is 0.2 to 5.0.
5. The resin composition according to claim 1, wherein the component (B) is selected from the group consisting of alumina, titania, zirconia, magnesia, barium titanate, zinc oxide, cerium oxide and calcium carbonate.
6. The resin composition according to claim 1, further comprising (D) a thermoplastic resin.
7. The resin composition according to claim 6, wherein the weight average molecular weight of the component (D) is 10000 or more.
8. The resin composition according to claim 6, wherein the component (D) is a thermoplastic resin having a transmittance of 80% or more for light having a wavelength of 450nm incident from the film surface when the film is formed into a film of 20 μm in the vertical direction.
9. The resin composition according to claim 6, wherein the component (D) is selected from the group consisting of a phenoxy resin, an acrylic resin and a polyphenylene ether resin.
10. The resin composition according to claim 1, wherein the content of the component (A) is 10 to 35% by mass, based on 100% by mass of nonvolatile components in the resin composition.
11. The resin composition according to claim 1, wherein the content of the component (B) is 25 to 40% by mass, based on 100% by mass of nonvolatile components in the resin composition.
12. The resin composition according to claim 1, wherein the content of the component (C) is 15 to 35% by mass, based on 100% by mass of nonvolatile components in the resin composition.
13. The resin composition according to claim 1, wherein the mass ratio of the component (A) to the total of the components (B) and (C), (the mass of the component (A)/(the mass of the components (B) and (C)), is 0.1 to 1.0.
14. The resin composition according to claim 1, wherein a cured product of the resin composition has an elongation of 2% or more measured at 25 ℃ in accordance with JIS K7161.
15. The resin composition according to claim 1, which is used for light reflection.
16. A cured product of the resin composition according to any one of claims 1 to 15.
17. A resin sheet comprising a support and a resin composition layer provided on the support and formed of the resin composition according to any one of claims 1 to 15.
18. A reflective sheet comprising a cured product of the resin composition according to any one of claims 1 to 15.
19. A printed circuit board comprising the reflective sheet of claim 18 as an interlayer insulating layer or a solder resist layer.
CN202111063372.5A 2020-09-11 2021-09-10 Resin composition Pending CN114163772A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975563A (en) * 2022-12-05 2023-04-18 江门嘉钡电子科技有限公司 High-reflectivity glue and novel glass substrate structure

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115975563A (en) * 2022-12-05 2023-04-18 江门嘉钡电子科技有限公司 High-reflectivity glue and novel glass substrate structure
CN115975563B (en) * 2022-12-05 2024-02-27 江门嘉钡电子科技有限公司 High-reflectivity glue and glass substrate structure

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