CN105482442A - Halogen-free resin composition and cover film prepared from the same - Google Patents
Halogen-free resin composition and cover film prepared from the same Download PDFInfo
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- CN105482442A CN105482442A CN201511033744.4A CN201511033744A CN105482442A CN 105482442 A CN105482442 A CN 105482442A CN 201511033744 A CN201511033744 A CN 201511033744A CN 105482442 A CN105482442 A CN 105482442A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
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Abstract
The invention relates to the technical field of flexible circuit boards, in particular to a halogen-free resin composition. The halogen-free resin composition comprises, by weight, 40-60 parts of polyester-type polyurethane resin, 15-25 parts of polyfunctional epoxy resin, 10-20 parts of phosphorus-containing phenolic resin, 15-25 parts of phosphorus-containing flame retardant and a proper quantity of organic solvent. The polyester-type polyurethane resin contains carboxyl, the acid value is 35 KOHmg/g, and the number-average molecular weight is 10,000-50,000. The polyester-type polyurethane resin containing the carboxyl can be reacted with biphenyl type epoxy resin, and the biphenyl type epoxy resin can be reacted with the phosphorus-containing phenolic resin so that an interpenetrating polymer network structure can be formed. In this way, a cured product has excellent ionic migration resistance and has high flexibility and high heat resistance. The invention further relates to a cover film prepared from the halogen-free resin composition, the excellent ionic migration resistance is achieved, and dendritic crystals can be avoided during ionic migration resistance testing.
Description
Technical field
The present invention relates to flexible electric circuit board technical field, particularly relate to the flexible electric circuit board mulch film of a kind of halogen-free resin composition and making thereof.
Background technology
Along with the densification of flexible electric circuit board, the live width/distance between centers of tracks (L/S) of sheet material has been developed to 50 μm/50 μm, even reaches 25 μm/25 μm.Distance between centers of tracks is more and more narrow, proposes requirements at the higher level to the insulating reliability of flexible circuit base material, and specific requirement has excellent resistance to ion transport; And after being tested by resistance to ion transport, not only require that insulation resistance touches the mark, also requirement can not have dendrite.The process of growth of dendrite is divided into dissolving, ion migration and deposition three step, under electric field action, the digestion of metallic ion of anode obtains electron reduction to cathode motion, negative electrode copper face is oxidized the electronics anode motion lost, isolator at leisure between circuit is assembled becomes crystallisate and settling, is formed " the dendritic growth thing " that moved by negative electrode anode.
Mulch film is a kind of important flexible circuit base material, for covering flexible electric circuit board outside surface, play welding resistance effect, and prevent circuit not by the pollution of dust, moisture and pharmaceutical chemicals and the infringement of other form, there is certain flexibility and enhancement simultaneously, the impact of conductor stress in BENDING PROCESS can be reduced, improve the resistance to deflection of flexible printed-circuit board.Common mulch film on Kapton, applies one deck tackiness agent form, improve the resistance to ion transport of mulch film, key improves the resistance to ion transport of tackiness agent (resin combination), and conventional tackiness agent is the epoxy adhesive of carboxy nitrile rubber toughening modifying; Because carboxy nitrile rubber uses the multiple auxiliary agents such as initiator, emulsifying agent, conditioning agent when synthesizing, make residual sodium ion in product, potassium ion and hydrolysis chlorion plasma impurity, cause the mulch film adopting carboxy nitrile rubber to change raw epoxy adhesive all can occur dendrite when resistance to ion transport test.
Japanese Patent JP2010-144081, JP2010-248380A, JP2010-018676A, US Patent No. 7820740B2, US7820741B2, US7722950B2, Chinese patent CN1865382 etc., IXE series inorganic ion exchanger (ion capturing agent) Japanese Toagosei Co., Ltd produced is added in mulch film carboxylic acrylonitrile butadiene rubber modified epoxy resin composition, can improve the resistance to ion transport of resin combination.Japanese Patent JP2003-165898 adopts a kind of high purity carboxy nitrile rubber (PNR-1H) toughened halogen-free epoxy resin, there is the Nitrogen-containing Phenolic Resins of certain flame retardant resistance for solidifying agent, the consumption of the hydrophilic phosphonium flame retardant of suitable reduction and aluminium hydroxide, the fire-proof resin composition of preparation for making mulch film, by 85%, the resistance to ion transport test of 85%RH, DC100V, 1000h.Although adopt mulch film prepared by these measures, after resistance to ion transport test, insulation resistance can meet the demands, and through the present inventor's testing authentication, takes mulch film prepared by these measures, all dendrite can occur when resistance to ion transport test.
For solving the problem, a kind of new resin combination now need be provided to make mulch film to solve the problem of dendrite growth.
Summary of the invention
For above-mentioned prior art deficiency, an object of the present invention is to provide a kind of halogen-free resin composition;
Two of object of the present invention is to provide a kind of mulch film adopting above-mentioned halogen-free resin composition to make, this mulch film is Halogen, fire-retardant, there is excellent resistance to ion transport, and can not dendrite be grown, this mulch film has that excessive glue amount is low, cementability is high in addition, snappiness and good heat resistance, flame retardant resistance reach the features such as UL94V-0.
To achieve these goals, technical scheme of the present invention is as follows:
A kind of halogen-free resin composition, by weight, comprising: polyester urethane resin 40 ~ 60 parts, polyfunctional epoxy resin 15 ~ 25 parts, phosphorus containing phenolic resin 10 ~ 20 parts, phosphonium flame retardant 15 ~ 25 parts and organic solvent are appropriate; Containing carboxyl in wherein said polyester urethane resin, acid number is 35KOHmg/g, number-average molecular weight is 10000 ~ 50000, it has outstanding resistance to ion transport, snappiness and hyperergy, particularly carboxyl wherein can react with epoxy resin, makes cured product combination of flexibility and thermotolerance.
Halogen-free resin composition of the present invention adopts carboxylic polyester urethane resin to be main toughened resin, coordinate biphenyl type epoxy resin, phosphorus containing phenolic resin, phosphonium flame retardant and organic solvent composition, wherein carboxylic polyester urethane resin can react with biphenyl type epoxy resin, biphenyl type epoxy resin and phosphorus containing phenolic resin react, to form interpenetrating polymer networks structure, make to obtain cured product and not only there is excellent resistance to ion transport, and there is high snappiness and thermotolerance.
Preferably, described PAUR is the UR-3500 that Co., Ltd.'s manufacture is spun by Japanese Japan; Its solid weight part consumption is 40 ~ 60 weight parts, and consumption is too many, and described halogen-free resin composition cross-linking density will be caused lower, and thermotolerance declines; Consumption very little, will cause the snappiness of described halogen-free resin composition and cementability to decline, and cause the mulch film made glue amount of overflowing to increase.
Preferably, described polyfunctional epoxy resin is one or both or the two or more mixture in phenol type novolac epoxy, ortho-cresol type novolac epoxy, bisphenol A-type novolac epoxy, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, tetrafunctional epoxy resin; Described polyfunctional epoxy resin can improve the cross-linking density of resin curing system, and then improves thermotolerance and the chemical resistant properties of resin combination; Preferred biphenyl type epoxy resin, epoxy equivalent (weight) is 285 ± 20g/eq, and this biphenyl type epoxy resin not only has outstanding thermotolerance, also has certain snappiness and flame retardant resistance.
Particularly, described phosphorus containing phenolic resin as fire retardant and the solidifying agent as epoxy resin, has high thermotolerance with the epoxy resin of its solidification in resin combination; The LC-950PM60 that XTW-92741, Shin-A company that commercial phosphorus containing phenolic resin has DOW company to manufacture manufactures, the good LC-950PM60 of preferred over-all properties, wherein phosphorus mass content about 9%.
Particularly, described phosphonium flame retardant, reaches halogen-free flameproof as making the resin combination after solidification; When it is for the preparation of mulch film, its addition except affecting flame retarding efficiency, also on excessive glue amount, stripping strength, shelf lives, be heated whether have impact to surface transport for a long time; Conventional phosphonium flame retardant has OP-930, OP-935 (German Clariant Corporation manufactures), SPB-100 (manufacture of Ben Otsuka Chemical Co., Ltd), the less and OP-935 that flame retarding efficiency is higher of preferable particle size.
Preferably, described halogen-free resin composition also comprises curing catalyst 0.1 ~ 0.3 weight part, described curing catalyst is imidazoles curing catalyst, for a kind of in glyoxal ethyline, 1-1-cyanoethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-undecyl imidazole, 1-cyanoethyl-2-undecyl imidazole, heptadecyl imidazole, two or more; Preferred 2-ethyl-4-methylimidazole.
Particularly, described organic solvent be one in acetone, butanone, pimelinketone, ethyl acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, dimethyl formamide, two or more; It can dissolving cured promotor, is mainly used in the solid content regulating halogen-free resin composition, to regulate the resin adhesive liquid viscosity of preparation.
A kind of mulch film adopting halogen-free resin composition described above to prepare, described mulch film comprises Kapton is formed at described Kapton side adhesive layer by described halogen-free resin composition, the thickness of wherein said adhesive layer is 5 ~ 45 μm, and the thickness of described Kapton is 10 ~ 100 μm.
Preferably, the thickness of described adhesive layer is 10 ~ 35 μm.
Preferably, also comprise laminating separate-type paper on described adhesive layer, the thickness of described separate-type paper is 50 ~ 150 μm.
The making method of this mulch film comprises the steps: described halogen-free resin composition (solid content 30wt% ~ 70wt%) to be coated in the wherein one side of described Kapton, this is coated with the Kapton baking semicure of halogen-free resin composition, obtains described mulch film.
The mulch film that halogen-free resin composition of the present invention makes, dendrite is there will not be when resistance to ion transport test, there is excellent resistance to ion transport, and have that excessive glue amount is low, cementability is high, snappiness and good heat resistance, flame retardant resistance reach the advantages such as UL94VTM-0.
Embodiment
For further setting forth the technique means and effect thereof that the present invention takes, be described in detail below in conjunction with the preferred embodiments of the present invention.
Embodiment 1
Halogen-free resin composition, by weight, comprise: polyester urethane resin (UR-3500, solids content 40%, acid number 35KOHmg/g) 40 solid weight parts, biphenyl type epoxy resin (NC-3000H, epoxy equivalent (weight) 285 ± 20g/eq, solids content 100%) 15 parts, phosphorus containing phenolic resin (LC-950PM60, solids content 60%) 10 solid weight parts, 2-ethyl-4-methylimidazole 0.1 part, phosphonium flame retardant (OP-935) 15 parts and appropriate solvent butanone;
The preparation of halogen-free resin composition (resin adhesive liquid): take above-mentioned each component by formula ratio, biphenyl type epoxy resin and 2-ethyl-4-methylimidazole is dissolved in advance with butanone, mix with other component again, make resin adhesive liquid, make its solid content be 40%;
The preparation of flexible electric circuit board mulch film: adopting coating machine this resin adhesive liquid to be coated in thickness is on the Kapton of 12.5 μm, controlling gluing (dry glue) thickness is 15 μm, toast 3 minutes in 160 DEG C of baking ovens subsequently, with the adhesive layer of forming section crosslinking curing on Kapton, then by this adhesive layer and separate-type paper laminating, obtained described mulch film.
Embodiment 2
Halogen-free resin composition, by weight, comprise polyester urethane resin (UR-3500, acid number 35KOHmg/g, solid content 40%) solid weight 60 parts, biphenyl type epoxy resin (NC-3000H, epoxy equivalent (weight) 285 ± 20g/eq, solid content 100%) 25 parts, phosphorus containing phenolic resin (LC-950PM60, solid content 60%) 20 solid weight parts, 2-ethyl-4-methylimidazole 0.3 part; Phosphonium flame retardant (OP-935) 25 parts and appropriate solvent butanone;
The preparation of halogen-free resin composition (resin adhesive liquid): take above-mentioned each component by formula ratio, biphenyl type epoxy resin and 2-ethyl-4-methylimidazole is dissolved in advance with butanone, mix with other component again, make resin adhesive liquid, make its solid content be 40%;
The preparation of flexible electric circuit board mulch film: adopting coating machine this resin adhesive liquid to be coated in thickness is on the Kapton of 12.5 μm, controlling gluing (dry glue) thickness is 15 μm, toast 3 minutes in 160 DEG C of baking ovens subsequently, with the adhesive layer of forming section crosslinking curing on Kapton, then by this adhesive layer and separate-type paper laminating, obtained described mulch film.
Embodiment 3
Halogen-free resin composition, by weight, comprise polyester urethane resin (UR-3500, acid number 35KOHmg/g, solid content 40%) 50 solid weight parts, biphenyl type epoxy resin (NC-3000H, epoxy equivalent (weight) 285 ± 20g/eq, solid content 100%) 20 parts, phosphorus containing phenolic resin (LC-950PM60, solid content 60%) 15 solid weight parts, 2-ethyl-4-methylimidazole 0.2 part, phosphonium flame retardant (OP-935) 20 parts and appropriate solvent;
The preparation of halogen-free resin composition (resin adhesive liquid): take above-mentioned each component by formula ratio, biphenyl type epoxy resin and 2-ethyl-4-methylimidazole is dissolved in advance with butanone, mix with other component again, make resin adhesive liquid, make its solid content be 40%;
The preparation of flexible electric circuit board mulch film: adopting coating machine this resin adhesive liquid to be coated in thickness is on the Kapton of 12.5 μm, controlling gluing (dry glue) thickness is 15 μm, toast 3 minutes in 160 DEG C of baking ovens subsequently, with the adhesive layer of forming section crosslinking curing on Kapton, then by this adhesive layer and separate-type paper laminating, obtained described mulch film.
Comparative example 1
Halogen-free resin composition, by weight, comprise polyester urethane resin (UR-3500, acid number 35KOHmg/g, solid content 40%) 70 solid weight parts, biphenyl type epoxy resin (NC-3000H, epoxy equivalent (weight) 285 ± 20g/eq, solid content 100%) 15 parts, phosphorus containing phenolic resin (LC-950PM60, solid content 60%) 10 solid weight parts, 2-ethyl-4-methylimidazole 0.2 part, phosphonium flame retardant (OP-935) 20 parts and appropriate solvent butanone;
The preparation of halogen-free resin composition (resin adhesive liquid): take above-mentioned each component by formula ratio, biphenyl type epoxy resin and 2-ethyl-4-methylimidazole is dissolved in advance with butanone, mix with other component again, make resin adhesive liquid, make its solid content be 40%;
The preparation of flexible electric circuit board mulch film: adopting coating machine this resin adhesive liquid to be coated in thickness is on the Kapton of 12.5 μm, controlling gluing (dry glue) thickness is 15 μm, toast 3 minutes in 160 DEG C of baking ovens subsequently, with the adhesive layer of forming section crosslinking curing on Kapton, then by this adhesive layer and separate-type paper laminating, obtained described mulch film.
Comparative example 2
Halogen-free resin composition, by weight, comprises polyester urethane resin (UR-3500, acid number 35KOHmg/g, solid content 40%) 30 solid weight parts, biphenyl type epoxy resin (NC-3000H, epoxy equivalent (weight) 285 ± 20g/eq, solid content 100%) 25 parts; Phosphorus containing phenolic resin (LC-950PM60, solid content 60%) 20 solid weight parts, 2-ethyl-4-methylimidazole 0.2 part, phosphonium flame retardant (OP-935) 20 parts and appropriate solvent;
The preparation of halogen-free resin composition (resin adhesive liquid): take above-mentioned each component by formula ratio, biphenyl type epoxy resin and 2-ethyl-4-methylimidazole is dissolved in advance with butanone, mix with other component again, make resin adhesive liquid, make its solid content be 40%;
The preparation of flexible electric circuit board mulch film: adopting coating machine this resin adhesive liquid to be coated in thickness is on the Kapton of 12.5 μm, controlling gluing (dry glue) thickness is 15 μm, toast 3 minutes in 160 DEG C of baking ovens subsequently, with the adhesive layer of forming section crosslinking curing on Kapton, then by this adhesive layer and separate-type paper laminating, obtained described mulch film.
Comparative example 3
Mulch film resin combination, by weight, comprise carboxy nitrile rubber (Nipol1072CG, wherein acrylonitrile content 27 quality %, solid content 100%, Zeon company manufactures) 35 parts, biphenyl type epoxy resin (NC-3000H, epoxy equivalent (weight) 285 ± 20g/eq, solid content 100%) 25 parts, bisphenol A type epoxy resin (EPIKOTEResin1001, epoxy equivalent (weight) 450-500g/eq, Mai Tu company manufactures) 40 parts, 4, 4 '-diaminodiphenylsulfone(DDS) (manufacture of A Tu company) 5 parts, 2-ethyl-4-methylimidazole 0.2 part, phosphonium flame retardant (OP-935) 25 parts and ion capturing agent (IXE-100, Toagosei Co., Ltd manufactures) 3 parts and appropriate solvent butanone.
The preparation of mulch film resin combination: dissolve carboxy nitrile rubber, biphenyl type epoxy resin, bisphenol A type epoxy resin and 2-ethyl-4-methylimidazole with butanone in advance, mix with other component again, be 40% with butanone solvent regulator solution solid content, make this resin combination.
The preparation of mulch film: adopting coating machine this resin combination to be coated in thickness is on the Kapton of 12.5 μm, controlling gluing (dry glue) thickness is 15 μm, toast 3 minutes in 160 DEG C of baking ovens subsequently, with the adhesive layer of forming section crosslinking curing on Kapton, then by this adhesive layer and separate-type paper laminating, obtained described mulch film.
The mulch film that above-described embodiment and comparative example obtain is carried out performance test, and its performance data is compared as follows shown in table 1.
Table 1
The testing method of above characteristic is as follows:
(1) excessive glue amount: according to the test of IPC-TM-6502.3.17.1 method, provide absolute value;
(2) stripping strength: according to IPC-TM-6502.4.9 method test, first by mulch film and 18 microns of rolled copper foil light faces laminating, test again after solidification;
(3) resistance to dip solderability: to test according to IPC-TM-6502.4.13;
(4) incendivity: measure according to UL94 vertical combustion;
(5) resistance to ion transport: get SF2010512SE (SHENGYI SCI.TECH's trade names) glue-free single-face flexibility copper-clad board and etch L/S=75/100 comb shape measurement circuit, by mulch film pressing on the line, be heating and curing, make sample.Test processes condition is temperature 85 DEG C, relative humidity 85%, applies volts DS 100V, sentences failure of insulation when wire insulation resistance is less than 1M Ω; If the test duration reaches 1000h, wire insulation resistance is still greater than 1M Ω then by test;
(6) dendrite: get the sample after the test of resistance to ion transport, observe under 40 power microscopes between circuit and whether have " dendritic growth thing ".
From upper table 1, the mulch film adopting halogen-free resin composition of the present invention to prepare has excellent resistance to ion transport, and dendrite is there will not be after ion migration test, but its shortcoming is, when resin combination wherein coordinates not good, as comparative example 1 and comparative example 2, although its resistance to ion migration ability is better, and also there is not dendrite, but excessive colloidality and resistance to dip solderability in can not meet existing requirement, therefore, halogen-free resin composition of the present invention not only requires the collocation of its carboxylic polyester urethane resin and other components, also require that its each component is made into ratio, the mulch film had compared with dominator could be obtained.
Halogen-free resin composition of the present invention adopts carboxylic polyester urethane resin to be main toughened resin in sum, coordinate biphenyl type epoxy resin, phosphorus containing phenolic resin, phosphonium flame retardant and organic solvent composition, wherein carboxylic polyester urethane resin can react with biphenyl type epoxy resin, biphenyl type epoxy resin and phosphorus containing phenolic resin react, to form interpenetrating polymer networks structure, make to obtain cured product and not only there is excellent resistance to ion transport, and there is high snappiness and thermotolerance.
The mulch film that halogen-free resin composition of the present invention makes, dendrite is there will not be when resistance to ion transport test, there is excellent resistance to ion transport, and have that excessive glue amount is low, cementability is high, snappiness and good heat resistance, flame retardant resistance reach the features such as UL94VTM-0.
Above-described embodiment, just preferred embodiment of the present invention, is not used for limiting the scope of the present invention, therefore all equivalences done with the structure described in the claims in the present invention, feature and principle change or modify, and all should be included within the claims in the present invention scope.
Claims (10)
1. a halogen-free resin composition, is characterized in that, by weight, comprising: polyester urethane resin 40 ~ 60 parts, polyfunctional epoxy resin 15 ~ 25 parts, phosphorus containing phenolic resin 10 ~ 20 parts, phosphonium flame retardant 15 ~ 25 parts and organic solvent are appropriate; Containing carboxyl in wherein said polyester urethane resin, acid number is 35KOHmg/g, and number-average molecular weight is 10000 ~ 50000.
2. halogen-free resin composition according to claim 1, is characterized in that: described polyfunctional epoxy resin be in phenol type novolac epoxy, ortho-cresol type novolac epoxy, bisphenol A-type novolac epoxy, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, tetrafunctional epoxy resin one or both or several.
3. halogen-free resin composition according to claim 2, is characterized in that: described polyfunctional epoxy resin is biphenyl type epoxy resin, and its epoxy equivalent (weight) is 285 ± 20g/eq.
4. halogen-free resin composition according to claim 1, is characterized in that: also comprise curing catalyst 0.1 ~ 0.3 part, and described curing catalyst is imidazoles curing catalyst.
5. halogen-free resin composition according to claim 1, is characterized in that: described organic solvent be in acetone, butanone, pimelinketone, ethyl acetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, dimethyl formamide one or both or several.
6. one kind adopts the mulch film that as described in any one of Claims 1 to 5 prepared by halogen-free resin composition.
7. mulch film according to claim 6, it is characterized in that: described mulch film comprises Kapton and is formed at the adhesive layer of described Kapton side by described halogen-free resin composition, the thickness of wherein said adhesive layer is 5 ~ 45 μm, and the thickness of described Kapton is 10 ~ 100 μm.
8. mulch film according to claim 7, is characterized in that: the thickness of described adhesive layer is 10 ~ 35 μm.
9. mulch film according to claim 7, it is characterized in that, its making method comprises the steps: to be coated on by described halogen-free resin composition in the wherein one side of described Kapton, this is coated with the Kapton baking semicure of resin combination, obtains described mulch film.
10. mulch film according to claim 7, it is characterized in that: also comprise laminating separate-type paper on described adhesive layer, the thickness of described separate-type paper is 50 ~ 150 μm.
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| CN201511033744.4A CN105482442A (en) | 2015-12-31 | 2015-12-31 | Halogen-free resin composition and cover film prepared from the same |
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| CN201511033744.4A Pending CN105482442A (en) | 2015-12-31 | 2015-12-31 | Halogen-free resin composition and cover film prepared from the same |
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| CN106633789A (en) * | 2016-09-30 | 2017-05-10 | 无锡市明盛强力风机有限公司 | Halogen-free flame retardant TPU film and preparation method thereof |
| CN107674388A (en) * | 2017-09-12 | 2018-02-09 | 广东生益科技股份有限公司 | Halogen-free resin composition and glued membrane prepared therefrom, cover layer and copper-clad plate |
| CN107799201A (en) * | 2017-10-25 | 2018-03-13 | 苏州巨峰电气绝缘系统股份有限公司 | The halogen-free flameproof of the resistance to gear box oil slot insulation material of motor in electric automobile and its application |
| CN107804043A (en) * | 2017-10-25 | 2018-03-16 | 苏州巨峰电气绝缘系统股份有限公司 | Suitable for wind-driven generator or the slot insulation material of motor in electric automobile and its application |
| CN107867035A (en) * | 2017-10-25 | 2018-04-03 | 苏州巨峰电气绝缘系统股份有限公司 | A kind of H of resistance to gear box oil levels slot insulation material and its application |
| CN107880530A (en) * | 2017-12-25 | 2018-04-06 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover layer and preparation method thereof |
| CN107901556A (en) * | 2017-11-03 | 2018-04-13 | 苏州巨峰电气绝缘系统股份有限公司 | It is a kind of to be suitable for wind-powered electricity generation and the dispensing insulating paper of solar energy transformer and its application |
| CN108183007A (en) * | 2017-12-22 | 2018-06-19 | 苏州巨峰电气绝缘系统股份有限公司 | One kind is used for F grades of slot insulation materials of nuclear power or transformer halogen-free flameproof and preparation method and application |
| CN108183008A (en) * | 2017-12-22 | 2018-06-19 | 苏州巨峰电气绝缘系统股份有限公司 | One kind is used for H grades of slot insulation materials of nuclear power or transformer halogen-free flameproof and preparation method and application |
| CN108676475A (en) * | 2018-05-15 | 2018-10-19 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, flexible printed-circuit board cover film, flexibility coat copper plate and preparation method thereof |
| CN108864924A (en) * | 2018-07-04 | 2018-11-23 | 湖北恒驰电子科技有限公司 | A kind of halogen-free resin composition and the flexible printed-circuit board cover film prepared with it |
| CN110819100A (en) * | 2019-11-15 | 2020-02-21 | 安徽德科科技有限公司 | High-thermal-stability circuit board material and preparation method thereof |
| CN111040387A (en) * | 2019-12-28 | 2020-04-21 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN114686131A (en) * | 2021-12-30 | 2022-07-01 | 江西优钛新材料科技有限公司 | high-Tg cover film and preparation method thereof |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633789A (en) * | 2016-09-30 | 2017-05-10 | 无锡市明盛强力风机有限公司 | Halogen-free flame retardant TPU film and preparation method thereof |
| CN107674388A (en) * | 2017-09-12 | 2018-02-09 | 广东生益科技股份有限公司 | Halogen-free resin composition and glued membrane prepared therefrom, cover layer and copper-clad plate |
| CN107799201A (en) * | 2017-10-25 | 2018-03-13 | 苏州巨峰电气绝缘系统股份有限公司 | The halogen-free flameproof of the resistance to gear box oil slot insulation material of motor in electric automobile and its application |
| CN107804043A (en) * | 2017-10-25 | 2018-03-16 | 苏州巨峰电气绝缘系统股份有限公司 | Suitable for wind-driven generator or the slot insulation material of motor in electric automobile and its application |
| CN107867035A (en) * | 2017-10-25 | 2018-04-03 | 苏州巨峰电气绝缘系统股份有限公司 | A kind of H of resistance to gear box oil levels slot insulation material and its application |
| CN107901556A (en) * | 2017-11-03 | 2018-04-13 | 苏州巨峰电气绝缘系统股份有限公司 | It is a kind of to be suitable for wind-powered electricity generation and the dispensing insulating paper of solar energy transformer and its application |
| CN108183008A (en) * | 2017-12-22 | 2018-06-19 | 苏州巨峰电气绝缘系统股份有限公司 | One kind is used for H grades of slot insulation materials of nuclear power or transformer halogen-free flameproof and preparation method and application |
| CN108183007A (en) * | 2017-12-22 | 2018-06-19 | 苏州巨峰电气绝缘系统股份有限公司 | One kind is used for F grades of slot insulation materials of nuclear power or transformer halogen-free flameproof and preparation method and application |
| CN107880530A (en) * | 2017-12-25 | 2018-04-06 | 广东生益科技股份有限公司 | Halogen-free resin composition and cover layer and preparation method thereof |
| CN107880530B (en) * | 2017-12-25 | 2020-10-27 | 广东生益科技股份有限公司 | Halogen-free resin composition, cover film and preparation method thereof |
| CN108676475A (en) * | 2018-05-15 | 2018-10-19 | 广东生益科技股份有限公司 | A kind of halogen-free resin composition, flexible printed-circuit board cover film, flexibility coat copper plate and preparation method thereof |
| CN108676475B (en) * | 2018-05-15 | 2021-02-09 | 广东生益科技股份有限公司 | Halogen-free resin composition, covering film for flexible printed circuit board, flexible copper clad laminate and preparation method thereof |
| CN108864924A (en) * | 2018-07-04 | 2018-11-23 | 湖北恒驰电子科技有限公司 | A kind of halogen-free resin composition and the flexible printed-circuit board cover film prepared with it |
| CN108864924B (en) * | 2018-07-04 | 2020-10-27 | 湖北恒驰电子科技有限公司 | Halogen-free resin composition and cover film for flexible printed circuit board prepared from same |
| CN110819100A (en) * | 2019-11-15 | 2020-02-21 | 安徽德科科技有限公司 | High-thermal-stability circuit board material and preparation method thereof |
| CN111040387A (en) * | 2019-12-28 | 2020-04-21 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN111040387B (en) * | 2019-12-28 | 2022-06-03 | 广东生益科技股份有限公司 | Halogen-free resin composition and flexible copper clad laminate comprising same |
| CN114686131A (en) * | 2021-12-30 | 2022-07-01 | 江西优钛新材料科技有限公司 | high-Tg cover film and preparation method thereof |
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Application publication date: 20160413 |