CN103074019A - Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same - Google Patents
Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same Download PDFInfo
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- CN103074019A CN103074019A CN2013100258767A CN201310025876A CN103074019A CN 103074019 A CN103074019 A CN 103074019A CN 2013100258767 A CN2013100258767 A CN 2013100258767A CN 201310025876 A CN201310025876 A CN 201310025876A CN 103074019 A CN103074019 A CN 103074019A
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Abstract
The invention discloses a halogen-free epoxy adhesive. The halogen-free epoxy adhesive is prepared from the following components in part by weight: 10-80 parts of special epoxy resin, 10-80 parts of bisphenols A epoxy resin, 10-40 parts of rubber-modified epoxy resin, 10-50 parts of toughener, 1-30 parts of curing agent, 0.01-1.0 part of curing promoter, 0-80 parts of inorganic filler, 1-40 parts of phosphor-containing flame-retardant agent, 1-40 parts of oxygen-containing flame-retardant agent and 0.01-1.0 part of antioxidant. The components are dispersed in organic solvent according to the mixture ratio to obtain the adhesive with the solid content of 30-50 percent by weight. The halogen-free epoxy adhesive provided by the invention has no halogen and uses phosphor and nitrogen flame-retardant agents to be coordinated with a flame-retardant adhesive system, so that the consumption of the phosphor-containing flame-retardant agent is reduced, the cost is reduced and the negative effect brought by a large amount of phosphor flame-retardant agent is overcome. The invention further discloses a flexible copper-clad plate using the halogen-free epoxy adhesive. The flame-retardant performance of the flexible copper-clad plate reaches UL94V-0 grade; and the halogen-free epoxy adhesive has the advantages of lower water absorption, excellent stripping strength, heat resistance, chemistry resistance and processing performance.
Description
Technical field
The invention belongs to the polymer composite Application Areas, be specifically related to the flexibility coat copper plate that a kind of Halogen epoxy adhesive prepares and use its preparation.
Background technology
The flexible copper-clad board industry, in order to guarantee the UL flame retardant rating of material, always with brominated Resins, epoxy with contain bromine addition and reach fire-retardant purpose, but there is the hidden danger of the dioxin that produces carcinogenic substance in discarded electronic apparatus when burning.Enforcement along with European Union's " about waste electronic andelectrical equipment instruction " (WEEE Waste Electrical and Electronic Equipment Directive) and " about being limited in the instruction of using some objectionable constituent in the electronic and electrical equipment " (RoHS Restriction ofHazardous Substances) two instructions has proposed to contain the requirement of the environmental management materials such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl, Poly Brominated Diphenyl Ethers to electronic product.For the megatrend of the environmental protection of satisfying the Halogen material, each producer is all at active development Halogen material.
Flexibility coat copper plate is non-halogen to have become trend, and halogen-free flameproof can use units such as containing phosphorus, nitrogen, silicon in the tackiness agent usually to realize.Halogen flexibility coat copper plate in the market mainly uses the phosphor-containing flame-proof system, the characteristics of its prescription are the Resins, epoxy with thermoplastic resin or rubber toughened phosphorous epoxy resin or specific groups, described specific groups Resins, epoxy comprises biphenyl type epoxy resin and dicyclopentadiene type Resins, epoxy, add simultaneously the mineral filler assisting flame-resistants such as phosphonium flame retardant and a certain amount of aluminium hydroxide, adopt DDS or resol as the solidifying agent of Resins, epoxy.But there is the uneven flexibility coat copper plate performance that affects of fillers dispersed on the one hand in the adding of a large amount of phosphorus flame retardants; A large amount of phosphorus is the adding of filler on the other hand, causes the mechanical properties decrease, thermotolerance of flexibility coat copper plate to reduce, and water-absorbent increases, and exists follow-up use procedure small molecular filler to ooze out to the surface or move, and affects follow-up use.And addition type phosphor-containing flame-proof and higher, a large amount of cost of manufacture that adds affiliation raising flexibility coat copper plate of prevailing price.
Summary of the invention
The object of the present invention is to provide a kind of not halogen-containing, use phosphorus, nitrogen combustion inhibitor cooperative flame retardant adhesive system, reduce the consumption of phosphonium flame retardant, reduced the cost of tackiness agent, solve because a large amount of phosphorus fire retardant adds the counter productive of bringing, prepare a kind of thermotolerance, high reliability with good flame retardant resistance, excellence, keep the preferably Halogen epoxy adhesive of mechanical property.
Another object of the present invention is to provide a kind of flexibility coat copper plate that uses above-mentioned production of adhesive, and its flame retardant resistance reaches the UL94V-0 level, has lower water-intake rate, excellent stripping strength, thermotolerance, chemical resistant properties and processing characteristics.
Technical scheme of the present invention is: a kind of Halogen epoxy adhesive, this tackiness agent is comprised of each component of following parts by weight: 10～80 parts of special epoxy resins, 10～80 parts of bisphenol A type epoxy resins, 10～40 parts of rubber modified epoxy resins, 10～80 parts of butyronitrile, 1～30 part in solidifying agent, 0.01～1.0 part of curing catalyst, 0～80 part of mineral filler, 1～40 part of phosphonium flame retardant contains 1～40 part of nitrogen combustion inhibitor, 0.01～1.0 part in oxidation inhibitor, by said ratio each component is scattered in the organic solvent, obtains the tackiness agent that solid content is 30wt%～50wt%.
As preferably, special epoxy resin is biphenyl type epoxy resin, dicyclopentadiene type Resins, epoxy or both mixtures.The Resins, epoxy carbon yield of these two kinds of structures is all higher, can reach preferably fire retardation.
As preferably, described rubber modified epoxy resin is the liquid nbr carboxyl terminal modified epoxy, and use therein Resins, epoxy comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin and hydride; Described nbr carboxyl terminal is the copolymer rubber of acrylonitrile and butadiene, and wherein the content of rubber is 15-80%.Utilize the nbr carboxyl terminal modified epoxy can strengthen the consistency of matrix resin and rubber, also has a certain amount of small molecules Resins, epoxy in the rubber modified epoxy resin simultaneously, also can increase the cross-linking density of cured article, improve the force of cohesion of glue-line, help to improve the stripping strength of flexibility coat copper plate.
As preferably, described paracril is the multipolymer of acrylonitrile and butadiene, and wherein acrylonitrile content is 15wt%～50wt%, and the copolymer molecule chain end is by carboxylated, and the copolymer rubber of vinyl cyanide, divinyl and carboxylic monomer.
As preferably, described solidifying agent is DDS, 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl oxide, 4, one or more in 4 '-diaminodiphenylmethane, the Dyhard RU 100.
As preferably, described curing catalyst is one or more in 1-Methylimidazole, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, boron trifluoride-amine complex, triphenylphosphine, the ureas promotor.
As preferably, described mineral filler is one or more in aluminium hydroxide, magnesium hydroxide, silicon-dioxide, light calcium carbonate, talcum powder, aluminium nitride, zinc oxide, aluminum oxide, mica, kaolin, the polynite.
As preferably, described phosphonium flame retardant is that described phosphonium flame retardant is one or more among SPB-100, OP-930, OP-935, the SP-703H as preferred.
As preferably, the described nitrogen combustion inhibitor that contains is among Melapur MC50, Melapur MC25, the Melapur MC15 one or more.
As preferably, described organic solvent is one or more in acetone, butanone, pimelinketone, ethyl acetate, toluene, ether, DMF, N,N-dimethylacetamide, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether.When the solid content of the tackiness agent that the preparation of interpolation organic solvent obtains is 30-50wt%, so that tackiness agent has viscosity, provide good processibility, present good coating effect.
Simultaneously the present invention also provides a kind of Halogen flexibility coat copper plate that uses above-mentioned production of adhesive, comprise polyimide film, be coated on the Halogen epoxy adhesive layer on the polyimide film and be laminated with Copper Foil on Halogen epoxy adhesive layer, the thickness of wherein said polyimide film is 8～100 μ m, the thickness of epoxy adhesive layer is 5～50 μ m, and the thickness of separate-type paper is 1/4～3Oz.
The preparation method of flexibility coat copper plate of the present invention is as follows:
The epoxy adhesive of above-mentioned preparation is coated on the Kapton by coating machine, and through the online dry baking oven, 80～170 ℃ of drying temperatures, heat-up time 2～10min, remove thus organic solvent, make adhesive segment reaction form the tackiness agent of semicure attitude, then lower and the Copper Foil roll-in is compound at 80～120 ℃, then this semicure state combination thing after fixing is namely made flexibility coat copper plate, the preferred temperature of after fixing is 100～180 ℃.
Beneficial effect of the present invention:
(1) tackiness agent of the present invention is environmentally friendly Halogen tackiness agent, and the objectionable impurities element such as not halogen-containing, stibnide does not pollute the environment, and meets the requirement of WEEE and RoSH instruction;
(2) tackiness agent of the present invention uses phosphorous epoxy resin, increase the flame retardant resistance of tackiness agent, use rubber modified epoxy resin, increased the consistency of toughner and Resins, epoxy, adopt phosphorus, nitrogen combustion inhibitor cooperative flame retardant adhesive system to reduce the consumption of phosphonium flame retardant, reduce the cost of manufacture of tackiness agent, improved the performance of tackiness agent;
(3) use the flexibility coat copper plate of this production of adhesive, flame retardant resistance reaches the UL94V-0 level, has excellent heat resistance, stripping strength, folding resistance and processing characteristics.
Embodiment
The present invention will be further described by the following examples.Starting material consumption and proportioning related among each embodiment are weight proportion, and each raw material is commercially available if no special instructions.
Embodiment 1
Get 20 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 12 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber bodies modified epoxy Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 15 parts, toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 30 parts, 4,4′ diaminodiphenyl sulfone 9.36 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN, four countries change into) 0.20 weight part; Aluminium hydroxide 20 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 5 parts; Contain 10 parts of nitrogen combustion inhibitor (Melapur MC15) weight; 0.20 part in oxidation inhibitor, the solid content of regulating tackiness agent with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Embodiment 2
Get 25 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 10 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber modified epoxy resin Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 20 part; 4,4′ diaminodiphenyl sulfone 9.02 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.20 weight part; Aluminium hydroxide 15 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) 7 weight parts; Contain nitrogen combustion inhibitor (Melapur MC15) 12 weight parts; 0.20 part in oxidation inhibitor; The solid content of regulating glue with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Embodiment 3
Get 32 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 15 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber modified epoxy resin Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 25 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 25 part; 4,4′ diaminodiphenyl sulfone 9.85 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.20 weight part; Aluminium hydroxide 25 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 10 parts; Contain 18 parts of nitrogen combustion inhibitor (Melapur MC15) weight; 0.20 part in oxidation inhibitor; The solid content of regulating glue with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Embodiment 4
Get 25 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 22 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber modified epoxy resin Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 33 part; 4,4′ diaminodiphenyl sulfone 10.62 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.30 weight part; Aluminium hydroxide 35 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 10 parts; Contain 16 parts of nitrogen combustion inhibitor (Melapur MC15) weight; 0.30 part in oxidation inhibitor; The solid content of regulating glue with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Embodiment 5
Get 30 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 30 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber modified epoxy resin Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 30 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 35 part; 4,4′ diaminodiphenyl sulfone 12.35 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.35 weight part; Aluminium hydroxide 20 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 15 parts; Contain 25 parts of nitrogen combustion inhibitor (Melapur MC15) weight; 0.30 part in oxidation inhibitor; The solid content of regulating glue with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Comparing embodiment 1
Get 20 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 12 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber bodies modified epoxy Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 15 parts, toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 30 parts, 4,4′ diaminodiphenyl sulfone 9.36 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN, four countries change into) 0.20 weight part; Aluminium hydroxide 20 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 18 parts; 0.20 part in oxidation inhibitor, the solid content of regulating tackiness agent with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Comparing embodiment 2
Get 25 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 10 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber modified epoxy resin Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 20 part; 4,4′ diaminodiphenyl sulfone 9.02 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.20 weight part; Aluminium hydroxide 15 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) 22 weight parts; 0.20 part in oxidation inhibitor; The solid content of regulating glue with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
Comparing embodiment 3
Get 32 parts of dicyclopentadiene type Resins, epoxy (large Japanese ink Co., Ltd., epoxy equivalent (weight) 280g/eq) 15 weight parts, bisphenol A type epoxy resins (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight) 475g/eq); Rubber modified epoxy resin Epon Resin58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 25 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 25 part; 4,4′ diaminodiphenyl sulfone 9.85 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.20 weight part; Aluminium hydroxide 25 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 25 parts; 0.20 part in oxidation inhibitor; The solid content of regulating glue with butanone solvent is 40wt%, the mixed Halogen epoxy adhesive of making.
This tackiness agent is coated on glue on the thick Kapton of 12.5 μ m by coating machine, and the drying tunnel of putting into again 120 ℃ heated 4 minutes, formed the dried glue of semicure at Kapton, and the gauge control of dried glue is about 15 μ m.Then itself and 18 μ m rolled copper foil roll-ins are laminated with, put into 100～180 ℃ baking oven after fixing with being laminated with thing, make flexibility coat copper plate.
Detect stripping strength, anti-immersed solder, chemical resistant properties, flame retardant resistance, the absorptive performance of Halogen flexibility coat copper plate, concrete outcome sees Table 1.
The fundamental property of table 1 Halogen flexibility coat copper plate
In sum, Halogen tackiness agent of the present invention is not halogen-containing, adopts phosphorous nitrogenous cooperative flame retardant can reduce the consumption of phosphorus fire retardant, and can improve the over-all properties of tackiness agent.Flexibility coat copper plate with this production of adhesive has preferably stripping strength, anti-immersed solder and chemical resistant properties, lower water-intake rate, and the fire-retardant UL94V-0 level that reaches of flexibility coat copper plate.
Above embodiment, all can only think explanation of the present invention rather than restriction, therefore every foundation essence technology of the present invention or wherein component or content all still belong in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment does.
Claims (10)
1. Halogen epoxy adhesive, it is characterized in that, this tackiness agent is prepared from by each component of following parts by weight: 10～80 parts of special epoxy resins, 10～80 parts of bisphenol A type epoxy resins, 10～40 parts of rubber modified epoxy resins, 10～50 parts of paracrils, 1～30 part in solidifying agent, 0.01～1.0 part of curing catalyst, 0～80 part of mineral filler, 1～40 part of phosphonium flame retardant, contain 1～40 part of nitrogen combustion inhibitor, 0.01～1.0 part in oxidation inhibitor is scattered in each component in the organic solvent by said ratio, obtains the tackiness agent that solid content is 30wt%～50wt%.
2. Halogen epoxy adhesive according to claim 1, it is characterized in that, described rubber modified epoxy resin is the carboxyl end of the liquid acrylonitrile-butadiene rubber modified epoxy, and use therein Resins, epoxy comprises bisphenol A type epoxy resin and hydride, bisphenol f type epoxy resin and hydride; Described carboxyl end of the liquid acrylonitrile-butadiene rubber is the multipolymer fluid rubber of acrylonitrile and butadiene, and wherein the content of carboxyl end of the liquid acrylonitrile-butadiene rubber is 15wt%～80wt%.
3. Halogen epoxy adhesive according to claim 1, it is characterized in that, described paracril is the multipolymer of acrylonitrile and butadiene, wherein acrylonitrile content is 15wt%～50wt%, the copolymer molecule chain end is by carboxylated, and the copolymer rubber of vinyl cyanide, divinyl and carboxylic monomer.
4. Halogen epoxy adhesive according to claim 1 is characterized in that, described solidifying agent is 4,4 '-diaminodiphenylsulfone(DDS), 3,3 '-diaminodiphenylsulfone(DDS), 4,4 '-diaminodiphenyl oxide, 4, one or more in 4 '-diaminodiphenylmethane, the Dyhard RU 100.
5. Halogen epoxy adhesive according to claim 1, it is characterized in that, described curing catalyst is one or more in 1-Methylimidazole, glyoxal ethyline, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, boron trifluoride-amine complex, triphenylphosphine, the ureas promotor.
6. Halogen epoxy adhesive according to claim 1, it is characterized in that, described mineral filler is one or more in aluminium hydroxide, magnesium hydroxide, silicon-dioxide, light calcium carbonate, talcum powder, aluminium nitride, zinc oxide, aluminum oxide, mica, kaolin, the polynite.
7. Halogen epoxy adhesive according to claim 1 is characterized in that, described phosphonium flame retardant is one or more among SPB-100, OP-930, OP-935, the SP-703H.
8. Halogen epoxy adhesive according to claim 1 is characterized in that, the described nitrogen combustion inhibitor that contains is among Melapur MC50, Melapur MC25, the Melapur MC15 one or more.
9. Halogen epoxy adhesive according to claim 1, it is characterized in that, described organic solvent is one or more in acetone, butanone, pimelinketone, ethyl acetate, toluene, ether, DMF, N,N-dimethylacetamide, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether.
10. flexibility coat copper plate with Halogen epoxy adhesive claimed in claim 1 preparation, it is characterized in that, comprise polyimide film, be coated on the Halogen epoxy adhesive layer on the polyimide film and be pressed on Copper Foil on this Halogen epoxy adhesive layer, the thickness of wherein said polyimide film is 8～100 μ m, the thickness of epoxy adhesive layer is 5～50 μ m, Copper Foil is rolled copper foil, and specification is 1/4～3Oz.
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| CN103834343A (en) * | 2014-03-25 | 2014-06-04 | 阳新宏洋电子有限公司 | Epoxy resin adhesive for flexible copper-clad plate and preparation method for epoxy resin adhesive |
| CN104163030A (en) * | 2014-06-30 | 2014-11-26 | 铜陵浩荣华科复合基板有限公司 | A method of manufacturing a halogen-free high-conductivity high-heat resistance copper-clad metal substrate |
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| CN111995976A (en) * | 2020-09-07 | 2020-11-27 | 上海闰龙电子材料有限公司 | Formula of halogen-free epoxy adhesive (heat-conducting adhesive) and preparation method thereof |
| CN112029461A (en) * | 2020-09-07 | 2020-12-04 | 上海闰龙电子材料有限公司 | Formula of halogen-free epoxy adhesive (structural adhesive) and preparation method thereof |
| CN113619234A (en) * | 2021-07-28 | 2021-11-09 | 山东滨芯电子科技有限公司 | Novel flexible copper-clad substrate material applied to high-frequency and high-speed transmission of 5G communication |
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| CN103694631A (en) * | 2013-11-14 | 2014-04-02 | 昆山珍实复合材料有限公司 | Halogen-free epoxy resin composition and cover film prepared by using halogen-free epoxy resin composition |
| CN103834343A (en) * | 2014-03-25 | 2014-06-04 | 阳新宏洋电子有限公司 | Epoxy resin adhesive for flexible copper-clad plate and preparation method for epoxy resin adhesive |
| CN103834343B (en) * | 2014-03-25 | 2015-06-17 | 阳新宏洋电子有限公司 | Epoxy resin adhesive for flexible copper-clad plate and preparation method for epoxy resin adhesive |
| CN104163030A (en) * | 2014-06-30 | 2014-11-26 | 铜陵浩荣华科复合基板有限公司 | A method of manufacturing a halogen-free high-conductivity high-heat resistance copper-clad metal substrate |
| CN104610709A (en) * | 2015-01-19 | 2015-05-13 | 珠海全宝电子科技有限公司 | High-Tg (glass transition temperature) high-thermal-dissipation aluminum-based CCL (copper-clad plate) used for automobile engine radiator |
| CN105368007A (en) * | 2015-12-23 | 2016-03-02 | 宁波康伯斯电器有限公司 | Epoxy resin composition |
| CN107722896A (en) * | 2017-10-25 | 2018-02-23 | 深圳市宝康电子材料有限公司 | A kind of modified epoxide resin adhesive |
| CN109096979A (en) * | 2018-08-15 | 2018-12-28 | 南昌正业科技有限公司 | A kind of adhesive and a kind of flexibility coat copper plate with high glass-transition temperature |
| CN111187588A (en) * | 2020-01-21 | 2020-05-22 | 汕头市骏码凯撒有限公司 | Insulating die bond adhesive for coating back surface of wafer and preparation method thereof |
| CN111961430A (en) * | 2020-07-10 | 2020-11-20 | 广东欣兴旺软板技术有限公司 | Sulfur-free flame-retardant adhesive |
| CN111995976A (en) * | 2020-09-07 | 2020-11-27 | 上海闰龙电子材料有限公司 | Formula of halogen-free epoxy adhesive (heat-conducting adhesive) and preparation method thereof |
| CN112029461A (en) * | 2020-09-07 | 2020-12-04 | 上海闰龙电子材料有限公司 | Formula of halogen-free epoxy adhesive (structural adhesive) and preparation method thereof |
| CN113619234A (en) * | 2021-07-28 | 2021-11-09 | 山东滨芯电子科技有限公司 | Novel flexible copper-clad substrate material applied to high-frequency and high-speed transmission of 5G communication |
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