CN101921557B - Halogen-free flame-retardant adhesive composition and flexible copper-clad plate using same - Google Patents
Halogen-free flame-retardant adhesive composition and flexible copper-clad plate using same Download PDFInfo
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- CN101921557B CN101921557B CN 201010268354 CN201010268354A CN101921557B CN 101921557 B CN101921557 B CN 101921557B CN 201010268354 CN201010268354 CN 201010268354 CN 201010268354 A CN201010268354 A CN 201010268354A CN 101921557 B CN101921557 B CN 101921557B
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Abstract
The invention discloses a halogen-free flame-retardant adhesive composition. The composition comprises the following components in part by weight: 15 to 45 parts of halogen-free epoxy resin, 15 to 60 parts of thermoplastic resin and/or synthetic rubber, 0.1 to 8 parts of curing agent and 5 to 60 parts of phosphorus-containing composite flame retardant. The invention also discloses a flexible copper-clad plate using the adhesive composition. The cured product of the adhesive composition provided by the invention shows high flame retardance, peeling strength, electric performance and welding heat resistance, does not comprise harmful substances or elements such as halogen, antimonide and the like and does not pollute environment; the flame retardant rating of the flexible copper-clad plate prepared from the composition of the invention reaches UL-94V0, and the flexible copper-clad plate also has the advantages of high heat resistance, high peeling strength, soldering resistance, no demixing after being subjected to dip soldering at the temperature of 300 DEG C for 1 minute and no bubbles; and because the halogen-free composition of the invention has high sticking performance, the speed of a production line can be increased and the production efficiency is improved.
Description
Technical field
The present invention relates to a kind of binder composition, relate in particular to a kind of halogen-free flame-retardant adhesive composition, the invention still further relates to the flexibility coat copper plate that uses said composition.
Background technology
In recent years, along with lightweight, miniaturization, the densification of electronic product, the increase in demand of various printed base plates, this performance to the copper-clad plate material has also proposed more strict requirement.At present, flame retardant type copper-clad plate materials'use a large amount of brominated Resins, epoxy and antimony compounds as fire retardant, but when the electronic product that uses this copper-clad plate to make is running into abnormal conditions burning or waste products and is burning, bromo-containing substance wherein and synergistic effect fire retardant antimonous oxide thereof, can produce toxic gas dioxin and hydrogen halide, environment and health of human body are worked the mischief.EU Committee has announced " instruction of waste and old electric electrical equipment " (being called for short " WEEEE instruction ") and " some objectionable impurities instruction is used in restriction in the electronic and electrical equipment " (being called for short " RoHS instruction "), requirement was from 1 day July in 2006, in the electronic and electrical equipment of newly putting on market, ban use of the objectionable impuritiess such as lead, mercury, antimony, sexavalent chrome, polybromodiphenyl ether and Polybrominated biphenyl.The enforcement of two instructions of European Union has clearly proposed the unleaded requirement of halogen in the printed wiring board manufacturing process.
Halogen-free flame-retardant copper-clad plate material is the flame retardant type copper-clad plate of the objectionable impuritiess such as not halogen-containing, plumbous, antimony.The Major Technology of realizing at present the flexibility coat copper plate halogen-free flame-retardant is with thermoplastic resin or rubber toughened phosphorous epoxy resin, add simultaneously the mineral filler assisting flame-resistants such as other fire retardants and a certain amount of aluminium hydroxide, adopt amino curing agent or resol as the solidifying agent of phosphorous resin.But there are at present the problems such as the not good and base material of fillers dispersed inequality and material mechanical performance and Copper Foil bounding force be inadequate.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free flame-retardant adhesive composition, said composition is not halogen-containing, and has good flame retardant resistance, binding property and mechanical property.
The present invention also aims to provide the flexibility coat copper plate that uses above-mentioned halogen-free flame-retardant adhesive composition.
First purpose of the present invention realizes by following technical measures: a kind of halogen-free flame-retardant adhesive composition, and it comprises the component of following weight part:
Halogen Resins, epoxy 15-45 part
Thermoplastic resin and/or synthetic rubber 15-60 part
Solidifying agent 0.1-8 part
Phosphorous composite flame-retardant agent 5-60 part.
Halogen Resins, epoxy described in the present invention refers to not comprise halogen atom in molecular structure, for example do not comprise bromine, but comprises the Resins, epoxy of at least two epoxy group(ing) in each molecule.The present invention has no particular limits halogen Resins, epoxy resin, can adopt the various halogen Resins, epoxy of selling on the market, such as the halogen Resins, epoxy that can select the types such as phenol type, biphenyl type, DCPD type, bisphenol A epoxide resin or bisphenol F epoxy resin and their hydride, wherein preferred dihydroxyphenyl propane (containing the modified bisphenol A type) Resins, epoxy and DPCD phenol-type epoxy resin.
Halogen Resins, epoxy of the present invention can also be the halogen phosphorous epoxy resin, described halogen phosphorous epoxy resin synthesizes by using the reactive phosphorus compound that phosphorus atom is bonded on the halogen Resins, epoxy, described reactive phosphorus compound comprises 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and is bonded in the compound of hydrogen atom on this compound phosphorus atom with the Resorcinol replacement.Described halogen phosphorous epoxy resin can adopt the various halogen phosphorous epoxy resins of selling on the market.
Various halogen Resins, epoxy above-mentioned among the present invention can use separately, also can be that two or more different halogen Resins, epoxy are used in combination.
The present invention can do following improvement: also contain the bisphenol A-type halogen Resins, epoxy of polybutadiene rubber and/or acrylic-nitrile rubber modification in the described halogen Resins, epoxy, its consumption is 5-45 part.
Thermoplastic resin of the present invention can adopt the applicable thermoplastic resin of market sale, preferably can select the thermoplastic resin of the suitable preparation fire retardant adhesives such as vibrin, acrylic resin, phenoxy resin and polyamide-imide resin.
Various thermoplastic resin of the present invention can use separately, also can be being used in combination of two or more different thermoplastic resins.
Synthetic rubber of the present invention adopts acrylonitrile butadiene copolymer usually, carboxylic acrylonitrile-butadiene rubber preferably wherein, the carboxylic paracril of this class is the rubber that the acrylonitrile and butadiene copolymerization generates, its copolymer molecule terminal carboxylization can by with comprising carboxyl, realize such as the monomer of methacrylic acid etc.Wherein acrylonitrile content is between 5-60 quality %, preferably between 20-30 quality %.Described carboxylic acrylonitrile-butadiene rubber can adopt the related products of market sale, as: the product XER-32 (JSR Corporation) of Nipol 1072 (Zeon Corporation), 1072CG (Nantex Industry Co., Ltd.) and high purity, low ionic impurity.The present invention can also adopt highly purified carboxylic acrylonitrile butadiene rubber, and is expensive, although therefore they can improve the bonding and ability of resisting to migration of tackiness agent effectively, also is difficult to a large amount of uses.
Various synthetic rubber of the present invention can use separately, also can be two or more different elastomeric being used in combination.
Thermoplastic resin of the present invention and synthetic rubber can also mix use, and at this moment, it is 10-30 part that thermoplastic resin accounts for weight part, and it is 10-30 part that synthetic rubber accounts for weight part.
The present invention does not have special requirement for restriction to the use of described solidifying agent, and any material that is typically used as epoxy curing agent can use, and wherein is preferably based on the solidifying agent of polyamines and/or the solidifying agent of acid anhydride-based.The solidifying agent based on polyamines that can select has diaminodiphenylsulfone(DDS), phenylenediamine, diaminodiphenyl-methane etc., and the solidifying agent of the acid anhydride-based that can select has Tetra hydro Phthalic anhydride, pyromellitic acid acid anhydride, hexahydrophthalic anhydride etc.Various solidifying agent of the present invention can use separately, also can be two or more be used in combination.
Phosphorous composite flame-retardant agent of the present invention is organo phosphorous compounds and/or organophosphate, can be preferably with the composition of soluble packing type fire retardant OP935 and organic soluble phosphonium flame retardant SPB-100 as fire retardant, the two mixes when using, and its weight part ratio is 1: 0.2-2.
The present invention can do following improvement: add mineral filler in the halogen-free flame-retardant adhesive composition.The present invention does not have special requirement for restriction to the kind of using mineral filler, and any filler for conventional flexible copper-clad panel material can use.From the consideration of fire-retardant auxiliary effect aspect, can use metal oxide, such as one or more the mixture in aluminium hydroxide, magnesium hydroxide, talcum powder, titanium dioxide, silicon-dioxide, calcium carbonate, zeolite, boron nitride, aluminium nitride, clay and the mica.The present invention is not particularly limited the consumption of above-mentioned mineral filler, but its consumption preferably at the 5-60 weight part, 20-35 weight part more preferably.
The present invention also can do following improvement: add the solidifying agent promotor of 0.1-1 weight part in the halogen-free flame-retardant adhesive composition, to accelerate the reaction between halogen-free epoxy resin and the solidifying agent.Solidifying agent promotor of the present invention can be adopted existing solidifying agent promotor of the prior art, wherein one or more mixing in preferred imidazolium compounds, three organic phosphine compounds, quaternary ammonium salt and the fluoroborate etc.Described imidazolium compounds can preferably adopt glyoxal ethyline, the 1-Methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 2-undecyl imidazole (C11Z), 1-cyanoethyl-2-undecyl imidazole (C11Z-CN) and 2-heptadecyl imidazoles (C17Z), above each glyoxaline compound can use separately, also can be that two or more mixing is used.Described three organic phosphine compounds can preferably adopt triphenylphosphine or tributylphosphine etc.Described quaternary ammonium salt can preferably adopt three (diethylacetic acid) salt of 2,4,6-three (dimethylamino methyl) phenol or three oleates of 2,4,6-three (dimethylamino methyl) phenol etc.Described fluoroborate can be selected one or more the mixture in the complex compound of complex compound, boron trifluoride and benzylamine of complex compound, boron trifluoride and n-Butyl Amine 99 of boron trifluoride and mono aminoethane and complex compound of boron trifluoride and xylidine etc.
The present invention can also add an amount of oxidation inhibitor, its addition 0.1-3 part.Described oxidation inhibitor preferably adopts polynary hindered phenol type antioxidant, such as antioxidant 1010, phosphite antioxidant 168 or phosphite antioxidant 626 etc. or their mixture.
Adopt above-mentioned halogen-free flame-retardant adhesive composition to prepare adhesive means: the consumption by above-mentioned each component takes by weighing halogen Resins, epoxy, thermoplastic resin and/or synthetic rubber, solidifying agent and phosphonium flame retardant, bisphenol A-type halogen Resins, epoxy that also can add as required polybutadiene rubber and/or acrylic-nitrile rubber modification etc. places the grinding plant such as sand mill, the adding organic solvent carries out mixed grinding, then delivers in the high-shear dispersed with stirring equipment to mix.Also can add according to actual needs solidifying agent promotor, mineral filler, oxidation inhibitor etc. fully mixes.Solids content preferably between 30～40 quality %, can obtain suitable viscosity in the tackiness agent that finally obtains, and good processibility is provided, to guarantee visual defects not occur in coating procedure.
Above-mentioned organic solvent can be one or more in acetone, butanone, pimelinketone, toluene, dimethylbenzene, N,N-dimethylacetamide, DMF, METHYLPYRROLIDONE, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether.
Second purpose of the present invention is to be achieved through the following technical solutions: a kind of flexibility coat copper plate, and it has electrical insulating film, bonding coat and Copper Foil, and described bonding coat is prepared from by above-mentioned halogen-free flame-retardant adhesive composition.
Described electrical insulating film is polyimide (PI) film or polyethylene terephthalate (PET) film, and thickness is 5-100 μ m.
Described Copper Foil can adopt electrolytic copper foil or rolled copper foil, and thickness can be between 1-100 μ m scope.
The dry thickness of described halogen-free flame-retardant adhesive composition constituting layer can be between 5-45 μ m scope.
Flexibility coat copper plate of the present invention is made and is comprised the steps:
(1) takes by weighing in proportion each component of above-mentioned halogen-free flame-retardant adhesive composition, place grinding plant, adding organic solvent carries out delivering in the high-shear dispersed with stirring equipment behind the mixed grinding and mixes, form the liquid dispersion of halogen-free flame-retardant adhesive composition, then use coating apparatus that this dispersion single or double is coated on the electrical insulating film, gluing thickness is 5-45 μ m;
(2) the electrical insulating film process drying oven that is coated with the binder composition dispersion in the step (1) is removed the halogen-free flame-retardant adhesive composition layer that organic solvent and dry adhesive composition cause its formation semicure attitude, drying temperature 80-180 ℃, be 2-10min heat-up time;
(3) under 80-120 ℃ temperature, electrical insulating film and Copper Foil roll-in with glue-line in the step (2) are applied ointment or plaster, then the single or double flexibility coat copper plate with semicure carries out after fixing, and the after fixing temperature is 60-180 ℃.
The present invention compared with prior art has following beneficial effect:
(1) cured product of halogen-free flame-retardant adhesive composition provided by the invention shows good flame retardant resistance, stripping strength, electrical property and welding thermotolerance, and the objectionable impurities element such as not halogen-containing, stibnide, does not pollute the environment;
(2) use the flexibility coat copper plate of halogen-free flame-retardant adhesive composition preparation of the present invention to have the following advantages:
1) flame retardant rating reaches the UL-94V0 level;
2) have good thermotolerance and high stripping strength;
3) soldering resistance, 300 ℃ of wicking 1min are not stratified, non-foaming;
4) because halogen of the present invention has the good performance that posts, enhance productivity so can increase the production linear speed.
Embodiment
The present invention will be further described by the following examples.Raw material consumption and proportioning related among each embodiment are the quality proportioning, each raw material if no special instructions, be commercially available, specified otherwise exception.
Each raw material choose that details are as follows:
1, halogen Resins, epoxy
Adopt the various halogen Resins, epoxy of selling on the market, for example: phenol type Resins, epoxy has: commodity are called FC Hard XI-1072 (Resinous Kasei Co., Ltd. epoxy equivalent (weight): 253g/eq).Biphenyl type epoxy resin has: NC-3000 (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 280g/eq).Bisphenol A epoxide resin has: GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq), GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq), KET4131A70 (KOLON, epoxy equivalent (weight): 215.5g/eq).Bisphenol F epoxy resin has: NC-2000-L (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 280g/eq).The bisphenol A type epoxy resin of polybutadiene rubber modification such as MX-257 (KanekaCoporation, CSR content 27 quality %, epoxy equivalent (weight): 294g/eq) and bisphenol A type epoxy resin such as HyPox RK 84L (the CVC Thermoset Specialties of acrylic-nitrile rubber modification, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) etc.
Can also adopt phosphorous epoxy resin can effectively be used to form the halogen-free flame-retardant adhesive composition, described phosphorous epoxy resin can adopt the various halogen Resins, epoxy of selling on the market, comprise 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and replace the compound be bonded in hydrogen atom on this compound phosphorus atom with Resorcinol.Gained the example of phosphorous epoxy resin have: ULE241P-K-70 (joins secondary Science and Technology Co., Ltd., epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %), STRUKTOL VP 3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: 4.5 quality %), PN-106 (Shanxi one chemical industry, epoxy equivalent (weight): 375g/eq, phosphorus content: 2.9 quality %).
Above halogen-free epoxy resin can use separately, perhaps is used in combination with two or more different resins.
2, thermoplastic resin
Can adopt the various thermoplastic resins of selling on the market, applicable thermoplastic resin has vibrin, acrylic resin, phenoxy resin and polyamide-imide resin.Selectable have a PPO*MX-90 (phenoxy resin, SABIC INNOVATIVE PLASTICS), Kayaflex series (polyamide-imide resin, Nippon Kayaku Co., Ltd.) and the KS series (acrylic resin that contains epoxy group(ing), Hitachi Chemical Co., Ltd.).
3, synthetic rubber
Synthetic rubber can adopt carboxylic acrylonitrile-butadiene rubber.The carboxylic paracril of this class is the rubber that the acrylonitrile and butadiene copolymerization generates, and selects the acrylonitrile butadiene copolymer of acrylonitrile content between 5-60 quality %.The preferred acrylonitrile butadiene copolymer of acrylonitrile content between 20-30 quality %.The object lesson of these commercially available carboxy-containing rubbers has Nipol 1072 (Zeon Corporation), 1072CG (Nantex Industry Co., Ltd.) and high purity, hangs down the product XER-32 (JSR Corporation) of ionic impurity.The present invention can also adopt highly purified carboxylic acrylonitrile butadiene rubber, and is expensive, although therefore they can improve the bonding and ability of resisting to migration of tackiness agent effectively, also is difficult to a large amount of uses.
Thermoplastic resin and synthetic rubber can be distinguished separately use, also can the two mix use.Thermoplastic resin that also can be two or more or two or more elastomeric being used in combination.
4, solidifying agent
The present invention does not have special requirement for restriction to the use of solidifying agent, and any material that is typically used as epoxy curing agent can use, and is preferably based on the solidifying agent of polyamines and the solidifying agent of acid anhydride-based.Wherein, based on what the solidifying agent of polyamines can be selected diaminodiphenylsulfone(DDS), phenylenediamine, diaminodiphenyl-methane arranged.The solidifying agent of acid anhydride-based can be selected Tetra hydro Phthalic anhydride, pyromellitic acid acid anhydride, hexahydrophthalic anhydride etc.Each above-mentioned solidifying agent can use separately, also can two or more be used in combination.
5, solidifying agent promotor
The object lesson of adoptable solidifying agent promotor can be selected imidazolium compounds, such as glyoxal ethyline, the 1-Methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-methylimidazole (2E4MZ), 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN), 2-undecyl imidazole (C11Z), 1-cyanoethyl-2-undecyl imidazole (C11Z-CN) and 2-heptadecyl imidazoles (C17Z); Can also select three organic phosphine compounds, such as triphenylphosphine, tributylphosphine etc.; Can also select quaternary ammonium salt or fluoroborate etc.
6, phosphonium flame retardant
Phosphonium flame retardant can select to adopt Organophosphorous compounds, such as phenolic group Alamos oligopolymer SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content are 13 quality %) etc.; Organophosphonate is such as dimethyl methyl phosphonate, diethyl ethylphosphate etc.; Organophosphate such as EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content are 23 quality %) etc., and phosphinate are such as alkali-metal phosphinate: phosphonous acid sodium or phosphonous acid potassium etc.
7, mineral filler
The present invention does not have special requirement for restriction to mineral filler, and any filler for conventional flexible copper-clad panel material can use.Especially, from the consideration of fire-retardant auxiliary effect aspect, can use metal oxide, such as one or more the mixture in aluminium hydroxide, magnesium hydroxide, talcum powder, titanium dioxide and silicon dioxide, calcium carbonate, zeolite, boron nitride, aluminium nitride, clay and the mica.
8, organic solvent
The organic solvent that uses when the present invention is prepared into tackiness agent can be acetone, butanone, pimelinketone, toluene, dimethylbenzene, N, in N-N,N-DIMETHYLACETAMIDE, DMF, METHYLPYRROLIDONE, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether one or more.Amount of solid content can obtain suitable viscosity preferably at 30-40 quality % in the composition of making, and provides good processibility, to guarantee visual defects not occur in coating procedure.
9, oxidation inhibitor
The used oxidation inhibitor of the present invention is polynary hindered phenol type antioxidant such as antioxidant 1010, phosphite antioxidant 168,626 grades or its mixture
10, electrical insulating film
The present invention does not have special restriction to the electrical insulating film that is used for flexibility coat copper plate, and any thin-film material that is generally used for flexibility coat copper plate can use.The example of suitable electrical insulating film has polyimide film, polyethylene terephthalate film, polyether-ether-ketone film etc.Consider from the viewpoint of thermotolerance, dimensional stability and the mechanical characteristic of the copper-clad plate made, preferred polyimide film, its thickness is preferably at 10-100 μ m.
Describe in more detail the present invention such as following embodiment, but the present invention never is subjected to the restriction of following embodiment:
Embodiment 1
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 12 weight parts, FC Hard XI-1072 (Resinous Kasei Co., Ltd. epoxy equivalent (weight): 253g/eq) 9.3 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 7.5 weight parts; HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 6.0 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 27 weight parts; Diaminodiphenylsulfone(DDS) 5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; SPB-100 phosphonitrile fire retardant (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 15 weight parts; EXOLIT OP 935 Hypophosporous Acid, 50 fat chemical (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 9.5 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 7.5 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine with the halogen-free flameproof binder composition, coat-thickness is 12 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 100 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of rolled copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Embodiment 2
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 12 weight parts, FC Hard XI-1072 (Resinous Kasei Co., Ltd. epoxy equivalent (weight): 253g/eq) 9.3 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 7.5 weight parts; HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 6.0 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 20 weight parts; PPO*MX-90 (phenoxy resin, SABIC INNOVATIVE PLASTICS) 7 weight parts; Diaminodiphenylsulfone(DDS) 5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 9.5 weight parts; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 14 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 7.6 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 30%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine with the halogen-free flameproof binder composition, coat-thickness is 12 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 100 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of rolled copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Embodiment 3
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 5.8 weight parts, MX-257 (Kaneka Coporation, CSR content 27 quality %, epoxy equivalent (weight): 294g/eq) 29.8 weight parts, HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 4.5 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 20.3 weight parts; Diaminodiphenylsulfone(DDS) 5.5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 9.7 weight parts; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 15 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 7.6 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 38%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine with the halogen-free flameproof binder composition, coat-thickness is 12 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 100 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of electrolytic copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Embodiment 4
Halogen-free epoxy resin MX-257 (Kaneka Coporation, CSR content 27 quality %, epoxy equivalent (weight): 294g/eq) 33.9 weight parts, HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 5.1 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 15 weight parts; PPO*MX-90 (phenoxy resin, SABIC INNOVATIVE PLASTICS) 5 weight parts; Diaminodiphenylsulfone(DDS) 5.6 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 9.8 weight parts; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 15.4 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 8.0 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 38%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine with the halogen-free flameproof binder composition, coat-thickness is 12 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 100 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of rolled copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Embodiment 5
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 9.8 weight parts, FC Hard XI-1072 (Resinous Kasei Co., Ltd. epoxy equivalent (weight): 253g/eq) 9.6 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 6.5 weight parts; HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 5.2 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 25.3 weight parts; Diaminodiphenylsulfone(DDS) 4.54 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 15 weight parts; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 9.5 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 13.01 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
With coating machine this dispersion liquid is coated on the polyimide film that thickness is 12.5 μ m, coat-thickness is 13 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 120 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of electrolytic copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Embodiment 6
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 9.8 weight parts, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 246g/eq) 10 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 6.5 weight parts; HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 5.2 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 25.3 weight parts; Diaminodiphenylsulfone(DDS) 4.54 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 15 weight parts; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 9.5 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 13.01 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
With coating machine this dispersion liquid is coated on the polyimide film that thickness is 12.5 μ m, coat-thickness is 13 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 120 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of electrolytic copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Embodiment 7
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 9.8 weight parts, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 246g/eq) 10 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 6.5 weight parts; HyPoxRK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 5.2 weight parts, product XER-32 (JSR Corporation) 20 weight parts of high purity, low ionic impurity; Diaminodiphenylsulfone(DDS) 4.54 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 15 weight parts; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 9.5 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 13.01 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
With coating machine this dispersion liquid is coated on the polyimide film that thickness is 12.5 μ m, coat-thickness is 13 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 120 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of electrolytic copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Comparative Examples 1
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 12 weight parts, FC Hard XI-1072 (Resinous Kasei Co., Ltd. epoxy equivalent (weight): 253g/eq) 9.3 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 7.5 weight parts; HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 6.0 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 21 weight parts; Diaminodiphenylsulfone(DDS) 5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; SPB-100 (Otsuka Chemical Co., Ltd, phosphorus content 13 quality %) 15 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 13 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
With coating machine this dispersion liquid is coated on the polyimide film that thickness is 12.5 μ m, coat-thickness is 12 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 100 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of electrolytic copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Comparative Examples 2
Halogen-free epoxy resin GESR901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 475g/eq) 12 weight parts, FC Hard XI-1072 (Resinous Kasei Co., Ltd. epoxy equivalent (weight): 253g/eq) 9.3 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 7.5 weight parts; HyPox RK 84L (CVC Thermoset Specialties, the elasticity scale of construction 32 quality %, epoxy equivalent (weight): 1350g/eq) 6.0 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 20 weight parts; Diaminodiphenylsulfone(DDS) 5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2 weight part; EXOLIT OP 935 (Clariant Produkte (Deutschland) GmbH, phosphorus content 23 quality %) 14 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 13 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.3 weight part places sand mill with said components, add butanone solvent, the solids content of regulating composition is 38%, then carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition.
With coating machine this dispersion liquid is coated on the polyimide film that thickness is 12.5 μ m, coat-thickness is 12 μ m, then in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.Polyimide film is bonded together by heat pressure adhesive at 100 ℃ of lower roll-type laminating machinees that use with the surface of glue-line and a surface of rolled copper foil (thickness is 18 μ m), then will be laminated with thing and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexibility coat copper plate.
Below the performance of the flexibility coat copper plate of above-described embodiment and Comparative Examples gained is measured contrast, acquired results sees Table one:
1, measuring method:
Flame retardant resistance:
Carve processing flexibility coat copper plate laminating material by total eclipse and remove whole Copper Foil preparation burning samples.Then according to the flame retardant resistance of UL94-V0 vertical combustion method test sample.If sample satisfies the fire-retardant requirement of UL94-V0, sample is assessed as " good " and represents with symbol " zero ", otherwise, then be assessed as " poor " and use symbol " X " expression.
The welding thermotolerance:
Carry out the welding thermotolerance of test material according to IPC-6502.4.13, it is by downcutting 25cm2 size preparation specimen from the flexible copper-clad panel material, these specimen is melted at 300 ℃ tin soak 1min in bathing and measure.Bubble, layering do not appear in test sample, are judged to be " OK ".
Stripping strength:
According to the IPC-6502.4.9 method, the stripping strength of test Copper Foil.Concrete grammar is: forming width by the exposure etching on flexibility coat copper plate is the circuit of 1mm, then showing the minimum value of peeling off the required power of copper foil circuit on the direction that forms an angle of 90 degrees with the speed of 50mm/min with laminating material measuring under 25 ℃ the condition, and with this observed value as stripping strength.
The ageing resistance test
With after the etching for the circuit of 1mm was placed in 160 ℃ the air circulating oven after 8 hours, the bounding force of cool to room temperature test Copper Foil and base material.
By following table one as can be known, the composition of embodiment 1 to embodiment 7 preparation satisfies demand of the present invention, flexible copper-clad panel material with the production of phosphorous composite flame-retardant agent resin combination demonstrates good stripping strength (after normality and the ageing-resistant test), welding thermotolerance and flame retardant resistance, this halogen-free flameproof binder composition has good posting property simultaneously, has important prospects for commercial application.And be used alone phosphorous fire retardant in Comparative Examples 1 and 2, and when comparing with the flexibility coat copper plate that satisfies demand of the present invention, the flexibility coat copper plate Flame Retardancy of its gained can't satisfy the requirement of UL 94V0, and the aspect of performances such as ageing resistance and stripping strength are relatively poor.
The component of table one embodiment 1-7 and Comparative Examples 1-2 and performance
The present invention can summarize with other the specific form without prejudice to spirit of the present invention or principal character.Above-mentioned embodiment of the present invention all can only be thought explanation of the present invention rather than restriction, therefore every foundation essence technology of the present invention or composition component or content all belong in the scope of technical solution of the present invention any trickle modification, equivalent variations and modification that above embodiment does.
Claims (5)
1. a halogen-free flame-retardant adhesive composition is characterized in that, it comprises the component of following weight part:
Halogen Resins, epoxy 15-45 part
Synthetic rubber or thermoplastic resin and synthetic rubber 15-60 part
Solidifying agent 0.1-8 part
Phosphorous composite flame-retardant agent 5-60 part
Mineral filler 5-60 part
Solidifying agent promotor 0.1-1 part, described thermoplastic resin and synthetic rubber mix when using, the weight part of described thermoplastic resin is 10-30 part, described elastomeric weight part is 10-30 part, and described halogen Resins, epoxy is the halogen Resins, epoxy of phenol type, biphenyl type, DCPD phenol type, bisphenol A-type or Bisphenol F type and one or more the combination in their hydride and the halogen phosphorous epoxy resin; Described thermoplastic resin is one or more the combination in vibrin, acrylic resin, phenoxy resin and the polyamide-imide resin; Described synthetic rubber is that acrylonitrile content is at the acrylonitrile butadiene copolymer of 5-60 quality percentage composition; Described solidifying agent adopts based on the solidifying agent of polyamines and/or the solidifying agent of acid anhydride-based; Described phosphorous composite flame-retardant agent is the composition of OP935 and two kinds of phosphonium flame retardants of SPB-100, and the weight part ratio of the two is 1: 0.2-2.
2. halogen-free flame-retardant adhesive composition according to claim 1, it is characterized in that: also contain the bisphenol A-type halogen Resins, epoxy of polybutadiene rubber and/or acrylic-nitrile rubber modification in the described halogen Resins, epoxy, its consumption is 5-45 part.
3. halogen-free flame-retardant adhesive composition according to claim 2 is characterized in that: the mixture of one or more in described solidifying agent promotor employing imidazolium compounds, three organic phosphine compounds, quaternary ammonium salt, the fluoroborate.
4. halogen-free flame-retardant adhesive composition according to claim 3, it is characterized in that: it also comprises the antioxidant of 0.1-3 part.
5. flexibility coat copper plate, it has electrical insulating film, bonding coat and Copper Foil, it is characterized in that: described bonding coat is prepared from by the described halogen-free flame-retardant adhesive composition of each claim of claim 1-4.
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| US9346983B2 (en) | 2012-03-23 | 2016-05-24 | Dow Global Technologies Llc | Flame retardant structural epoxy resin adhesives and process for bonding metal members |
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