CN106046685B - High-peel-strength epoxy resin composition and application thereof - Google Patents
High-peel-strength epoxy resin composition and application thereof Download PDFInfo
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- CN106046685B CN106046685B CN201610589425.XA CN201610589425A CN106046685B CN 106046685 B CN106046685 B CN 106046685B CN 201610589425 A CN201610589425 A CN 201610589425A CN 106046685 B CN106046685 B CN 106046685B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 34
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 34
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 11
- 239000011574 phosphorus Substances 0.000 claims abstract description 11
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 10
- 239000005011 phenolic resin Substances 0.000 claims abstract description 10
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- ICQLQVWXFUWFRI-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)propanenitrile Chemical compound N#CC(C)N1C=CN=C1C ICQLQVWXFUWFRI-UHFFFAOYSA-N 0.000 claims description 12
- 230000002421 anti-septic effect Effects 0.000 claims description 12
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 12
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000004843 novolac epoxy resin Substances 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- MPDNQLRUMUIREC-UHFFFAOYSA-N 1-ethoxy-2-methylimidazole Chemical compound CCOn1ccnc1C MPDNQLRUMUIREC-UHFFFAOYSA-N 0.000 claims description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims 4
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000945 filler Substances 0.000 abstract description 4
- 239000003242 anti bacterial agent Substances 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 2
- JJWKKSUCSNDHNJ-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanol Chemical compound CC1=NC=CN1CCO JJWKKSUCSNDHNJ-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000013329 compounding Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- -1 Lauxite Polymers 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 230000000845 anti-microbial effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007719 peel strength test Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a high-peel-strength epoxy resin composition and application thereof, wherein the high-peel-strength epoxy resin composition is prepared from the following raw materials in parts by weight: 45-55 parts of flexible epoxy resin, 15-25 parts of dicyclopentadiene type phenolic epoxy resin, 23-33 parts of phosphorus-containing phenolic resin, 1-5 parts of 3,3' -diaminodiphenyl sulfone, 15-45 parts of toluene, 0.01-1 part of curing accelerator and 1-10 parts of inorganic antibacterial agent. The high-peel-strength epoxy resin composition has the advantages that the proper types and the proper amounts of the inorganic antibacterial agent and the curing accelerator are preferably selected through reasonable proportioning, the antibacterial property and the peel strength are improved, the comprehensive performance is very excellent, the filler dispersing effect is good, the cost is low, and the high-peel-strength epoxy resin composition is environment-friendly and economical.
Description
Technical field
The present invention relates to chemical technology fields more particularly to a kind of high peel strength epoxy resin composition and application thereof.
Background technique
With the developing trend multifunction of electronic product, the components of electronic product are also constantly to light, thin, short, small etc.
Aspect development, the especially extensive use of high density integrated circuit technology propose high performance, highly reliable to consumer electronic product
The requirement of property and high security；Good to industrial electronic product proposition technical performance, inexpensive, low energy consumption requirement.Therefore
The substrate copper-clad plate face of the core material of electronic product --- printed circuit board (Printed Circuit Board, abbreviation PCB)
Face higher technical requirements, severeer use environment and higher environmental requirement.
Copper-clad plate (Copper Clad Laminate, abbreviation CCL) is with fiber mainly for the production of printed circuit board
Paper, glass fabric or glass fibre non-woven (being commonly called as glass felt) etc. are used as reinforcing material, soak with resin, single or double covers
With copper foil, through a kind of product made of hot pressing.Existing copper-clad plate is due to manufacture raw material and the otherness of manufacture structure, CCL
The technical performance of substrate is different.
Resin liquid in copper-clad plate generally uses compositions of thermosetting resin.Thermosetting resin refers to that resin is heating, adding
It depresses or under curing agent, action of ultraviolet light, is chemically reacted, the major class that crosslinking curing becomes non-fusant matter synthesizes tree
Rouge.Common thermosetting resin have phenolic resin, Lauxite, melamine formaldehyde resin, epoxy resin, unsaturated-resin,
Polyurethane, polyimides etc..Thermosetting resin and curing agent, promotor, filler etc. form compositions of thermosetting resin, then through adjusting
Resin liquid is made for use in metal-clad foil plate.In order to make metal-clad foil plate that there is preferable insulation performance, usually in resin
Filler can be added in liquid.
Epoxy resin refers to containing two or more epoxy groups in molecule, with aliphatic, alicyclic or aromatic series
Equal organic compounds are skeleton, and can react generation three in the presence of chemical reagent appropriate (curing agent) by epoxy group
Tie up the general name of the compound of netted solidfied material.Epoxy resin is due to good chemical stability, electrical insulating property, corrosion-resistant
Property, caking property and mechanical strength, are widely used in the material of printed circuit board (PCB) as binder.
Therefore, those skilled in the art be dedicated to developing a kind of comprehensive technical performance it is excellent, but also with compared with high-vitrification
Transition temperature and antimicrobial composite material compared with high-peeling strength.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, technical problem to be solved by the invention is to provide a kind of high removings
Strength epoxy resin combination and application thereof.
Object of the present invention is to what is be achieved through the following technical solutions：
A kind of high peel strength epoxy resin composition, is prepared by the raw material of following weight parts：Flexible-epoxy
45-55 parts, 15-25 parts of dicyclopentadiene type novolac epoxy resin, 23-33 parts of phosphorus containing phenolic resin, 3,3'- diaminodiphenylsulfone
1-5 parts, 15-45 parts of toluene, 0.01-1 parts of curing accelerator, 1-10 parts of inorganic antiseptic.
Preferably, the inorganic antiseptic is wolframic acid silver, silver bromide, mixture one or more in silver orthophosphate.
It is highly preferred that the inorganic antiseptic is mixed by wolframic acid silver, silver bromide, silver orthophosphate, the wolframic acid silver, bromine
Change silver, the mass ratio of silver orthophosphate is (1-3)：(1-3)：(1-3).
Preferably, the curing accelerator be 2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole,
One or more mixture in 1- (beta-hydroxyethyl) -2-methylimidazole.
It is highly preferred that the curing accelerator is by 2,2 '-bis- (4,5- methylimidazoles), 1- cyanoethyl -2- methyl miaow
Azoles, 1- (beta-hydroxyethyl) -2-methylimidazole mix, described 2,2 '-bis- (4,5- methylimidazoles), 1- cyanoethyl -2- first
Base imidazoles, 1- (beta-hydroxyethyl) -2-methylimidazole mass ratio are (1-3)：(1-3)：(1-3).
Preferably, the partial size of the inorganic antiseptic is 0.01-20 μm.
Preferably, the flexible-epoxy can be produced using commercially available Dainippon Ink. & Chemicals Inc
Model EXA-4822 flexible-epoxy, epoxide equivalent 390g/eq.
Preferably, the dicyclopentadiene type novolac epoxy resin can use commercially available big Japanese ink chemical industry
The dicyclopentadiene type novolac epoxy resin of the model HP-7200L of Co., Ltd.'s production, epoxide equivalent 247g/eq.
Preferably, the phosphorus containing phenolic resin can be using the model of commercially available Dow Chemical Company production
For XZ92741 phosphorus containing phenolic resin, phosphorus content 9wt%.
The present invention also provides application of the above-mentioned high peel strength epoxy resin composition in preparation copper-clad plate.
The preparation method of copper-clad plate can be：By glass fabric in high peel strength epoxy resin composition of the invention
Middle dipping, is then dried at a certain temperature, is removed solvent and is carried out semi-solid preparation, obtains prepreg；Then above-mentioned preimpregnation is taken
Material one or more is superimposed together according to certain sequence, copper foil is covered respectively in the prepreg two sides being superimposed with each other, in heat
Solidify in press and copper-clad plate is made.
High peel strength epoxy resin composition of the invention preferably goes out suitable inorganic antibacterial by reasonably matching
Agent, curing accelerator type and dosage, improve anti-microbial property and peel strength, comprehensive performance is very excellent, filler dispersion
Effect is good, low in cost, environment friendly and economical.
Specific embodiment
The present invention will be further explained with reference to the examples below, as described below, is only to preferable implementation of the invention
Example, not limits the present invention, any person skilled in the art is possibly also with the disclosure above
Technology contents be changed to the equivalent embodiment changed on an equal basis.Without departing from the concept of the present invention, according to the present invention
Technical spirit any simple modification or equivalent variations that following embodiment is made, fall within the scope of protection of the present invention.
Each raw material introduction in embodiment：
Flexible-epoxy, using the flexibility of the model EXA-4822 of Dainippon Ink. & Chemicals Inc's production
Epoxy resin, epoxide equivalent 390g/eq.
Dicyclopentadiene type novolac epoxy resin, the model produced using Dainippon Ink. & Chemicals Inc
The dicyclopentadiene type novolac epoxy resin of HP-7200L, epoxide equivalent 247g/eq.
Phosphorus containing phenolic resin, the model XZ92741 phosphorus containing phenolic resin produced using Dow Chemical Company,
Phosphorus content is 9wt%.
3,3'- diaminodiphenylsulfones, No. CAS：599-61-1.
Toluene, No. CAS：108-88-3.
Wolframic acid silver, No. CAS：13465-93-5,0.1 μm of partial size.
Silver bromide, No. CAS：7785-23-1,0.1 μm of partial size.
Silver orthophosphate, No. CAS：7784-09-0,0.1 μm of partial size.
2,2 '-bis- (4,5- methylimidazoles), No. CAS：69286-06-2.
1- 1-cyanoethyl-2-methylimidazole, No. CAS：23996-55-6.
1- (beta-hydroxyethyl) -2-methylimidazole, No. CAS：1615-15-2.
Embodiment 1
High peel strength epoxy resin composition material (parts by weight)：50 parts of flexible-epoxy, dicyclopentadiene type phenol
20 parts of formaldehyde epoxy resin, 28 parts of phosphorus containing phenolic resin, 2.5 parts of 3,3'- diaminodiphenylsulfone, 20 parts of toluene, curing accelerator 0.3
Part, 3 parts of inorganic antiseptic.
The inorganic antiseptic is 1 by wolframic acid silver, silver bromide, silver orthophosphate in mass ratio:1:1 is uniformly mixed
It arrives.
The curing accelerator is by 2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (β-hydroxyl
Ethyl) -2-methylimidazole is 1 in mass ratio:1:1 is uniformly mixed to obtain.
The preparation of high peel strength epoxy resin composition：
By flexible-epoxy, dicyclopentadiene type novolac epoxy resin, toluene with 400 revs/min stir 5 minutes, then
Phosphorus containing phenolic resin, 3,3'- diaminodiphenylsulfone, curing accelerator is added to stir 10 minutes with 300 revs/min, is eventually adding nothing
Machine antibacterial agent is stirred 60 minutes with 300 revs/min.Obtain the high peel strength epoxy resin composition of the preparation of embodiment 1.
Copper-clad plate preparation：By glass fabric (the E grade glass fibers provided using Dongguan City Guang Hong composite material Co., Ltd
Tie up cloth 106, grammes per square metre 25g/m2, with a thickness of 0.03mm) and it is immersed in the high peel strength epoxy resin composition of the preparation of embodiment 1
In obtain impregnated cloth, control glass fabric content be 10wt% (content of glass fabric is 10wt% i.e. in impregnated cloth,
The content of high peel strength epoxy resin composition is 90wt%), then dipping is arranged in 100 DEG C of baking oven, toasts 2h,
Solvent is removed, prepreg is obtained；It is superimposed with each other to obtain substrate using five prepregs, covers 30 μm in two facing surfaces of substrate
Thick layers of copper (copper foil of the model TU25 provided using the golden one hundred product of rubber and plastic factory of Dongguan City end of the bridge) is laminated, and pressure is applied
400PSI, minimum temperature are 50 DEG C, and maximum temperature is 380 DEG C, are 3 DEG C/min heating with rate, after reaching 380 DEG C of maximum temperature
Keep 40min.Obtain the copper-clad plate of embodiment 1.
Embodiment 2
Substantially the same manner as Example 1, difference is only that：The inorganic antiseptic by silver bromide, silver orthophosphate in mass ratio
It is 1:1 is uniformly mixed to obtain.Obtain high peel strength epoxy resin composition and the copper-clad plate of embodiment 2.
Embodiment 3
Substantially the same manner as Example 1, difference is only that：The inorganic antiseptic by wolframic acid silver, silver orthophosphate in mass ratio
It is 1:1 is uniformly mixed to obtain.Obtain high peel strength epoxy resin composition and the copper-clad plate of embodiment 3.
Embodiment 4
Substantially the same manner as Example 1, difference is only that：The inorganic antiseptic by wolframic acid silver, silver bromide in mass ratio
It is 1:1 is uniformly mixed to obtain.Obtain high peel strength epoxy resin composition and the copper-clad plate of embodiment 4.
Embodiment 5
Substantially the same manner as Example 1, difference is only that：The curing accelerator is by 1- 1-cyanoethyl-2-methylimidazole, 1-
(beta-hydroxyethyl) -2-methylimidazole is 1 in mass ratio:1 is uniformly mixed to obtain.Obtain the high-peeling strength ring of embodiment 5
Epoxy resin composition and copper-clad plate.
Embodiment 6
Substantially the same manner as Example 1, difference is only that：The curing accelerator is by 2,2 '-bis- (4,5- dimethyl miaows
Azoles), 1- (beta-hydroxyethyl) -2-methylimidazole be in mass ratio 1:1 is uniformly mixed to obtain.Obtain the high removing of embodiment 6
Strength epoxy resin combination and copper-clad plate.
Embodiment 7
Substantially the same manner as Example 1, difference is only that：The curing accelerator is by 2,2 '-bis- (4,5- dimethyl miaows
Azoles), 1- 1-cyanoethyl-2-methylimidazole be in mass ratio 1:1 is uniformly mixed to obtain.Obtain the high-peeling strength of embodiment 7
Composition epoxy resin and copper-clad plate.
Test case 1
The glass transition temperature of copper-clad plate made from embodiment 1-7, peel strength are tested respectively.Test method
It is as follows：Glass transition temperature Tg：It is measured according to the DMA method of IPC-TM-6502.4.24 defined.Peel strength PS：
According to experiment condition " after thermal stress " in IPC-TM-6502.4.8 method, the peel strength of plate is tested.Concrete outcome is shown in Table 1.
Table 1：Glass transition temperature, peel strength test result table
Comparing embodiment 1 and embodiment 2-4, embodiment 1 (wolframic acid silver, silver bromide, silver orthophosphate compounding) glass transition temperature
Degree, peel strength test result are substantially better than embodiment 2-4 (wolframic acid silver, silver bromide, both any in silver orthophosphate compound)；Compare
Embodiment 1 and embodiment 5-7, embodiment 1 (2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (β-
Ethoxy) -2-methylimidazole compounding) glass transition temperature, peel strength test result be substantially better than embodiment 5-7 (2,2 ' -
It is both any multiple in bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (beta-hydroxyethyl) -2-methylimidazole
With).
Test case 2
The anti-microbial property of prepreg made from embodiment 1-7 is tested respectively.It is carried out by QB/T2591-2003 method
Measurement.Escherichia coli ATYCC 25922, staphylococcus aureus ATCC6538.Specific test result is shown in Table 2.
Table 2：Anti-microbial property test result table
Comparing embodiment 1 and embodiment 2-4, embodiment 1 (wolframic acid silver, silver bromide, silver orthophosphate compounding) anti-microbial property are obvious
Better than embodiment 2-4 (wolframic acid silver, silver bromide, both any compounding in silver orthophosphate)；Comparing embodiment 1 and embodiment 5-7 are implemented
Example 1 (2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (beta-hydroxyethyl) -2-methylimidazole compounding)
Anti-microbial property is substantially better than embodiment 5-7 (2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (β-hydroxyl
Ethyl) both any compounding in -2-methylimidazole).
Test case 3
Embodiment 1 and the resistance to electric arc of copper-clad plate made from embodiment 5-7 are tested respectively.Resistance to electric arc：By standard Q/
GDSY6050-20122.5.1 is tested.Specific test result is shown in Table 3.
Table 3：Insulation performance test result table
| Sample | Resistance to electric arc, Kv |
| Embodiment 1 | 151 |
| Embodiment 5 | 142 |
| Embodiment 6 | 140 |
| Embodiment 7 | 140 |
Comparing embodiment 1 and embodiment 5-7, embodiment 1 (2,2 '-bis- (4,5- methylimidazoles), 1- cyanoethyl -2- first
Base imidazoles, 1- (beta-hydroxyethyl) -2-methylimidazole compounding) insulation performance is substantially better than embodiment 5-7 (2,2 '-bis- (4,5- diformazans
Base imidazoles), 1- 1-cyanoethyl-2-methylimidazole, both any compounding in 1- (beta-hydroxyethyl) -2-methylimidazole).
Claims (3)
1. a kind of high peel strength epoxy resin composition, it is characterised in that：It is prepared by the raw material of following weight parts：It is flexible
45-55 parts of epoxy resin, 15-25 parts of dicyclopentadiene type novolac epoxy resin, 23-33 parts of phosphorus containing phenolic resin, 3,3'- diamino
1-5 parts of base diphenyl sulphone (DPS), 15-45 parts of toluene, 0.01-1 parts of curing accelerator, 1-10 parts of inorganic antiseptic；
The inorganic antiseptic is mixed by wolframic acid silver, silver bromide, silver orthophosphate, the wolframic acid silver, silver bromide, silver orthophosphate
Mass ratio is (1-3)：(1-3)：(1-3)；
The curing accelerator is by 2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (β-hydroxyl second
Base) -2-methylimidazole mixes, described 2,2 '-bis- (4,5- methylimidazoles), 1- 1-cyanoethyl-2-methylimidazole, 1- (β -
Ethoxy) -2-methylimidazole mass ratio be (1-3)：(1-3)：(1-3).
2. high peel strength epoxy resin composition as described in claim 1, it is characterised in that：The inorganic antiseptic
Partial size is 0.01-20 μm.
3. application of the high peel strength epoxy resin composition as described in claim 1 in preparation copper-clad plate.
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| CN106634280A (en) * | 2016-11-25 | 2017-05-10 | 雄子（上海）新材料科技有限公司 | Environment-friendly latex paint |
| CN106833085A (en) * | 2016-11-25 | 2017-06-13 | 雄子（上海）新材料科技有限公司 | Environmentally friendly elastic force anti-crack mastic powder |
| CN106630776A (en) * | 2016-11-25 | 2017-05-10 | 雄子（上海）新材料科技有限公司 | Environmental-friendly stone-like coating and preparation method thereof |
| CN106630823A (en) * | 2016-11-25 | 2017-05-10 | 雄子（上海）新材料科技有限公司 | Environment-friendly color riverstone paint |
| CN106675276B (en) * | 2016-11-25 | 2019-05-03 | 雄子（上海）新材料科技有限公司 | Environment-friendly interior wall coating |
| CN107057280A (en) * | 2016-12-26 | 2017-08-18 | 东莞市佳乾新材料科技有限公司 | A kind of composition epoxy resin and its manufacture method with antibacterial functions |
| CN110256809A (en) * | 2019-04-29 | 2019-09-20 | 深圳市嘉联兴科技有限公司 | A kind of preparation method of electronic cigarette components antibacterial and mouldproof material |
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| CN102010569A (en) * | 2010-07-16 | 2011-04-13 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and high-flexibility coating film prepared by same |
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| CN101280093A (en) * | 2008-05-13 | 2008-10-08 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate |
| CN102010569A (en) * | 2010-07-16 | 2011-04-13 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and high-flexibility coating film prepared by same |
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Denomination of invention: A high peel strength epoxy resin composite and its application Granted publication date: 20181130 Pledgee: Bank of Nanjing Co.,Ltd. Huai'an branch Pledgor: Huai'an Licheng New Material Co.,Ltd. Registration number: Y2024980017558 |