CN103045143A - Halogen-free epoxy adhesive and cover film prepared by using halogen-free epoxy adhesive - Google Patents
Halogen-free epoxy adhesive and cover film prepared by using halogen-free epoxy adhesive Download PDFInfo
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- CN103045143A CN103045143A CN2012104609753A CN201210460975A CN103045143A CN 103045143 A CN103045143 A CN 103045143A CN 2012104609753 A CN2012104609753 A CN 2012104609753A CN 201210460975 A CN201210460975 A CN 201210460975A CN 103045143 A CN103045143 A CN 103045143A
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Abstract
The invention discloses a halogen-free epoxy adhesive which is prepared from the following components in parts by weight: 10-80 parts of phosphorus-containing epoxy resin, 10-40 parts of rubber modified epoxy resin, 10-50 parts of a toughening agent, 1-25 parts of a curing agent, 0.01-1.0 part of a curing accelerant, 0-80 parts of inorganic filler, 1-40 parts of a phosphorus-containing fire retardant, 1-40 parts of a nitrogenous fire retardant and 0.01-1.0% of an antioxidant. According to the invention, the components are dispersed into an organic solvent according to the proportion, so that the adhesive with the solid content of 30-50wt% can be obtained. The halogen-free epoxy adhesive does not contain halogen, and uses the phosphorus-containing fire retardant and the nitrogenous fire retardant to cooperate with a flame-retardant adhesive system, thus reducing the dosage of the phosphorus-containing fire retardant, and overcoming the negative effect caused by using a great deal of phosphorus-containing fire retardant; the halogen-free epoxy adhesive is good in fire resistance, excellent in heat resistance, high in reliability and better in mechanical property. The invention also discloses a cover film prepared from the halogen-free epoxy adhesive, and the cover film has the fire resistance of UL 94V-0 level, excellent stripping strength, heat resistance and processing performance.
Description
Technical field
The invention belongs to the polymer composite Application Areas, be specifically related to a kind of Halogen epoxy adhesive and use the mulch film of its preparation.
Background technology
The packaged material that is used at present flexible PCB (FPC), 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 " (WEEEWaste 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 leadless process and Halogen material, each producer is all at active development Halogen material.
The packaged material of FPC 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 mulch film 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 mulch film 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 mulch film 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.
Summary of the invention
The technical problem to be solved in the present invention is for above-mentioned deficiency of the prior art, provide a kind of not halogen-containing, use phosphorus, nitrogen combustion inhibitor cooperative flame retardant adhesive system, reduce the consumption of phosphonium flame retardant, solve because a large amount of phosphorus fire retardant adds the counter productive of bringing, have thermotolerance, the high reliability of good flame retardant resistance, excellence, keep simultaneously the preferably Halogen epoxy adhesive of mechanical property.
Another technical problem that the present invention will solve is for above-mentioned deficiency of the prior art, and a kind of mulch film that uses above-mentioned production of adhesive is provided, and its flame retardant resistance reaches UL94 V-0 level, has excellent stripping strength, thermotolerance 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 phosphorous epoxy resins, 10～40 parts of rubber modified epoxy resins, 10～50 parts of toughner, 1～25 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%.
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 mulch film.
As preferably, described toughner is thermoplastic resin, synthetic rubber or both mixtures, and described thermoplastic resin is one or more in vibrin, acrylate resin, phenoxy resin, the polyamide-imide resin; Described synthetic rubber is the multipolymer of acrylonitrile and butadiene, and wherein acrylonitrile content is 15wt%～50wt%, and the copolymer molecule chain end is by carboxylated.
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 mulch film 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 separate-type paper 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 50～150 μ m.
The preparation method of mulch film 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, at drying temperature 80-170 ℃, heat-up time 2-10min, remove thus organic solvent, make adhesive segment reaction form the tackiness agent of semicure attitude, then 80-100 ℃ lower and separate-type paper is compound, namely obtain the Halogen mulch film.
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;
(3) use the mulch film of this production of adhesive, flame retardant resistance reaches UL94 V-0 level, has excellent heat resistance, stripping strength 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 phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 15 weight parts, rubber bodies modified epoxy Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 25 parts, toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 20 parts, 4,4′ diaminodiphenyl sulfone 7.26 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%) weight is 5 parts; Contain 5 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Embodiment 2
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 25 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 20 part; 4,4′ diaminodiphenyl sulfone 7.93 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) 5 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Embodiment 3
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 35 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 25 part; 4,4′ diaminodiphenyl sulfone 8.45 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 8 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Embodiment 4
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 45 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 25 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 30 part; 4,4′ diaminodiphenyl sulfone 10.82 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.30 weight part; Aluminium hydroxide 15 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; 0.30 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Embodiment 5
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 50 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 35 part; 4,4′ diaminodiphenyl sulfone 11.05 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN four countries change into) 0.30 weight part; Aluminium hydroxide 15 weight parts; Phosphonium flame retardant OP-935(Germany Clariant company, phosphorus content 23%) weight is 8 parts; Contain 5 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Comparing embodiment 1
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 15 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 25 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 20 part; 4,4′ diaminodiphenyl sulfone 7.26 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%) weight is 10 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Comparing embodiment 2
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 25 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 20 part; 4,4′ diaminodiphenyl sulfone 7.93 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%) weight is 15 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, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
Comparing embodiment 3
Phosphorous epoxy resin FX-305(TOHTO Chemical Industry Co., Ltd. epoxy equivalent (weight) 500g/eq) 35 weight parts; Rubber modified epoxy resin Epon Resin 58005(Hexion Specialty Chemicals, Inc., rubber content 40wt%) 20 parts; Toughner 1072CG(Zeon Corporation, acrylonitrile content 27wt%) 25 part; 4,4′ diaminodiphenyl sulfone 8.45 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 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 baking oven of putting into again 120 ℃ heated 4 minutes, and at the dried glue of Kapton formation semicure, the gauge control of dried glue is about 15 μ m.Then itself and separate-type paper are laminated with, rolling obtains Halogen mulch film product.
The performance of the excessive glue amount of detection Halogen mulch film, stripping strength, anti-immersed solder, water-intake rate, flame retardant resistance, concrete outcome sees Table 1.
The fundamental property of table 1 Halogen mulch film
Annotate: above-mentioned peel strength test method is pressed IPC-TM-650 2.4.9 standard testing, first mulch film and Copper Foil light face are laminated with, and under 170 ℃, pressing under the 2.5MPa/2min condition, again test after the curing.
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.Mulch film with this production of adhesive has preferably stripping strength and anti-immersed solder, lower water-intake rate, and the fire-retardant UL 94V-0 level that reaches of mulch film.
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 phosphorous epoxy resins, 10～40 parts of rubber modified epoxy resins, 10～50 parts of toughner, 1～25 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%.
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 toughner is thermoplastic resin, synthetic rubber or both mixtures, and described thermoplastic resin is one or more in vibrin, acrylate resin, phenoxy resin, the polyamide-imide resin; Described synthetic rubber 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.
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. mulch film 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 laminated with separate-type paper 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 50～150 μ m.
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