CN101875825A - 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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- CN101875825A CN101875825A CN2010101569793A CN201010156979A CN101875825A CN 101875825 A CN101875825 A CN 101875825A CN 2010101569793 A CN2010101569793 A CN 2010101569793A CN 201010156979 A CN201010156979 A CN 201010156979A CN 101875825 A CN101875825 A CN 101875825A
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Abstract
The invention discloses a halogen-free flame retardant adhesive composition, which comprises the following components in parts 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 nitrogen-containing flame retardant. The halogen-free flame retardant adhesive composition utilizes nitrogen-containing flame retardant, thus reducing the use of phosphonium flame retardant, in addition, the cured product shows good flame resistance, peel strength, electrical property and welding thermal resistance, does not contain elements of halogen, antimonide and other harmful substances and does not pollute the environment. The invention also discloses a flexible copper-clad plate, which is provided with an electrical insulating film, an adhesive coat and a copper foil, wherein the adhesive coat is prepared from the halogen-free flame retardant adhesive composition. The flame retardant rating of the flexible copper-clad plate is up to UL-94V0, thus the flexible copper-clad plate has good thermal resistance, adhesive force, soldering resistance and other performances.
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 flexible copper-clad 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 material has used 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 July 1st, 2006, in the electronic and electrical equipment of newly putting on market, ban use of 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 objectionable impuritiess such as not halogen-containing, plumbous, antimony.The major technique approach that realizes the flexible copper-clad plate halogen-free flame-retardant at present is with thermoplastic resin or rubber toughened phosphorous epoxy resin, add mineral filler assisting flame-resistants such as other P contained compounds and a certain amount of aluminium hydroxide simultaneously, adopt amino curing agent or resol solidifying agent as phosphorous resin.But owing to add a large amount of organic phosphorus flame retardants and other mineral fillers, the problem that in the process of preparation binder composition, has on the one hand the fillers dispersed inequality, not good and have base material and a not enough risk of Copper Foil bounding force with this material mechanical performance of making on the other hand.
Summary of the invention
First purpose of the present invention is to provide a kind of halogen-free flame-retardant adhesive composition, and said composition is not halogen-containing, and has excellent flame-retardant performance, binding property and mechanical property.
Second purpose of the present invention is to provide the flexible copper-clad 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:
15～45 parts of halogen Resins, epoxy
15～60 parts of thermoplastic resin and/or synthetic rubber
0.1～8 part in solidifying agent
Contain 5～60 parts of nitrogen combustion inhibitors.
Halogen Resins, epoxy described in the present invention is not comprise halogen atom in molecular structure, for example do not wrap bromated, but in each molecule, comprise the Resins, epoxy of at least two epoxy group(ing).The present invention has no particular limits halogen Resins, epoxy resin, the various halogen Resins, epoxy of selling on the market can be adopted, for example the halogen Resins, epoxy of types such as phenol type, biphenyl type, bisphenol A epoxide resin or bisphenol F epoxy resin and their hydride can be selected.Wherein preferred bisphenol A epoxide resin and biphenyl 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 phosphatization thing comprises 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound and replace the compound that is bonded in hydrogen atom on this compound phosphorus atom with Resorcinol.Described halogen phosphorous epoxy resin can adopt the various halogen phosphorous epoxy resins of selling on the market.
Various halogen Resins, epoxy described in the present invention can use separately, also can be that two or more different halogen Resins, epoxy are used in combination.
Thermoplastic resin of the present invention can adopt the thermoplastic resin that is suitable for of market sale, preferably can select the thermoplastic resin of suitable preparation fire retardant adhesives such as vibrin, acrylic resin, phenoxy resin and polyamide-imide resin.
Various thermoplastic resins described in 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, wherein preferably carboxylic acrylonitrile-butadiene rubber, the carboxylic paracril of this class is the rubber that the acrylonitrile and butadiene copolymerization generates, its copolymer molecule terminal carboxylization can realize as the monomer of methacrylic acid etc. by with comprising carboxyl.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: Nipol 1072 (Zeon Corporation), 1072CG (NantexIndustry Co., Ltd.) and the product XER-32 (JSR Corporation) of high purity, low ionic impurity.The present invention can also adopt highly purified carboxylic acrylonitrile butadiene rubber, costs an arm and a leg, although therefore they can improve the bonding and anti-migration performance of tackiness agent effectively, also is difficult to a large amount of uses.
Various synthetic rubber described in the present invention can use separately, also can be two or more different elastomeric being used in combination.
Thermoplastic resin described in the present invention and synthetic rubber can 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 used as epoxy curing agent usually 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 for use has diaminodiphenylsulfone(DDS), phenylenediamine and diaminodiphenyl-methane etc.; The solidifying agent of the acid anhydride-based that can select for use has Tetra hydro Phthalic anhydride, pyromellitic acid acid anhydride and hexahydrophthalic anhydride etc.Various solidifying agent of the present invention can use separately, also can be two or more be used in combination.
The nitrogen combustion inhibitor requirement nitrogen content that contains of the present invention usually in 15-30 quality % scope, preferably in 15-25 quality % scope, can select for use trimeric cyanamide, trimeric cyanamide urate etc. not phosphorated contain nitrogen combustion inhibitor.The described nitrogen combustion inhibitor that contains can also be selected nitrogenous polyphosphate compound for use, this compounds can provide superior flame retardant properties and not lose welding thermotolerance under the normal condition of solidifying product on the one hand to solidifying product, can improve the anti-migration performance of solidifying product on the other hand and do not lose welding thermotolerance under the moisture absorption condition, and halogen atom-containing not.The preferred trimeric cyanamide polyphosphate of described nitrogenous compound polyphosphate, or piperazine polyphosphate, or the mixture of trimeric cyanamide polyphosphate and piperazine polyphosphate.Described trimeric cyanamide polyphosphate can preferably adopt the melamine salt of melamine pyrophosphate, trimeric cyanamide triphosphate, trimeric cyanamide pentaphosphate or tetramethylolmethane phosphate ester acid etc.Described piperazine polyphosphate can be selected piperazine pyrophosphate salt, piperazine triphosphate, piperazine pentaphosphate or 2 for use, 4-diamino-6-diethoxy phosphoryl-1,3,5-triazines (DAPT) etc.Wherein nitrogenous compound polyphosphate is melamine pyrophosphate, piperazine pyrophosphate salt or the mixing of the two more preferably.Various fire retardants among the present invention can use separately, also can two or more combination of compounds use.
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 that is used for conventional flexible copper-clad panel material can use.Consideration from fire-retardant auxiliary effect aspect, can use metal oxide, as one or more the mixture in aluminium hydroxide, magnesium hydroxide, talcum powder, titanium dioxide, silicon-dioxide, lime 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, 20-40 weight part more preferably.
The present invention also can do following improvement: add solidifying agent promotor 0.1-1 weight part at 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, one or more mixing in wherein 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), more than 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 2,4, three (diethylacetic acid) salt or 2,4 of 6-three (dimethylamino methyl) phenol, three oleates of 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. for use.
The present invention also can do further improvement: add phosphonium flame retardant in the halogen-free flame-retardant adhesive composition, described phosphonium flame retardant can adopt Organophosphorous compounds as containing the synergistic fire retardant of nitrogen combustion inhibitor, as phenolic group Alamos oligopolymer etc.; Perhaps adopt Organophosphonate,, perhaps adopt phosphinate, for example alkali-metal phosphinate: phosphonous acid sodium or phosphonous acid potassium etc. as dimethyl methyl phosphonate or diethyl ethylphosphate etc.Described phosphonium flame retardant addition 5-15 weight part.
The present invention can also add an amount of oxidation inhibitor, its addition 0.1-3 weight part.Described oxidation inhibitor preferably adopts polynary hindered phenol type antioxidant, as antioxidant 1010, phosphite antioxidant 168 or phosphite antioxidant 626 etc. or their mixture.
Adopt above-mentioned halogen-free flame-retardant adhesive preparation of compositions adhesive means: the consumption by above-mentioned each component takes by weighing halogen Resins, epoxy, thermoplastic resin and/or synthetic rubber, solidifying agent and contains nitrogen combustion inhibitor, place grinding plant such as sand mill, the adding organic solvent carries out mixed grinding, delivers to then in the high-shear dispersed with stirring equipment to mix.Also can add solidifying agent promotor, mineral filler and phosphonium flame retardant according to actual needs and carry out thorough mixing.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 acetone, butanone, pimelinketone, toluene, dimethylbenzene, N,N-dimethylacetamide, N, one or more in dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, 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 flexible copper-clad plate, and it has electrical insulating film, bonding coat and Copper Foil, and described bonding coat is formed by above-mentioned halogen-free flame-retardant adhesive preparation of compositions.
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 the 1-100 mu m range.
The dry thickness of the layer that described halogen-free flame-retardant adhesive composition constitutes can be between the 5-45 mu m range.
Flexible copper-clad plate of the present invention is made and is comprised the steps:
(1) takes by weighing each component of above-mentioned halogen-free flame-retardant adhesive composition in proportion, 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, use coating apparatus that this dispersion single or double is coated on the electrical insulating film then, gluing thickness is 5-45um;
(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 80-170 ℃, be 2-10 minute heat-up time;
(3) under 80-120 ℃ temperature, electrical insulating film that has glue-line in the step (2) and Copper Foil roll-in are applied ointment or plaster, the single or double flexible copper-clad plate with semicure carries out after fixing then, and the after fixing temperature is 120-180 ℃.
The present invention compared with prior art has following beneficial effect:
(1) employing contains nitrogen combustion inhibitor in the halogen-free flame-retardant adhesive composition provided by the invention, reduced the use of phosphonium flame retardant, and show excellent flame-retardant performance, stripping strength, electrical property and welding thermotolerance at cured product, and objectionable impurities elements such as not halogen-containing, stibnide do not pollute the environment.
(2) use the flexible copper-clad plate of halogen-free flame-retardant adhesive preparation of compositions of the present invention to have the following advantages:
1) flame retardant rating reaches the UL-94V0 level.
2) have good thermotolerance and bounding force, MOT test (150 ℃, 10 days) stripping strength still has 0.49Kgf/cm.
3) soldering resistance, 300 ℃ of wicking 1min are not stratified, non-foaming.
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, the 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 XD-1000 (Nippon Kayaku Co., Ltd. epoxy equivalent (weight): 246g/eq).Biphenyl type epoxy resin has: NC-3000 (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 280g/eq).Bisphenol A epoxide resin has: and GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/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).
Can also adopt phosphorous epoxy resin can be used to form the halogen-free flame-retardant adhesive composition effectively, described phosphorous epoxy resin can adopt the various halogen Resins, epoxy of selling on the market, comprising 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound and replace the compound that is bonded in hydrogen atom on this compound phosphorus atom with Resorcinol.The example of described phosphorous epoxy resin has: ULE241P-K-70 (joins secondary Science and Technology Co., Ltd., epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %), STRUKTOL VP3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: PN-106 (Shanxi one chemical industry, epoxy equivalent (weight): 375g/eq, phosphorus content: 2.9 quality %) 4.5 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, suitable thermoplastic resin has vibrin, acrylic resin, phenoxy resin and polyamide-imide resin.Selectable have PPO*MX-90 (phenoxy resin, SABICINNOVATIVE PLASTICS), a Kayaflex series (polyamide-imide resin, Nippon Kayaku Co., Ltd.) and 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 have Nipol 1072 (Zeon Corporation), 1072CG (Nantex Industry Co., Ltd.) and the product XER-32 (JSR Corporation) of high purity, low ionic impurity.The present invention can also adopt highly purified carboxylic acrylonitrile butadiene rubber, costs an arm and a leg, although therefore they can improve the bonding and anti-migration performance of tackiness agent effectively, also is difficult to a large amount of uses.
Thermoplastic resin and synthetic rubber can be distinguished use separately, also can the two mix use.Also thermoplastic resin that 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 used as epoxy curing agent usually 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 for use diaminodiphenylsulfone(DDS), phenylenediamine, diaminodiphenyl-methane arranged.The solidifying agent of acid anhydride-based can be selected for use 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 for use, 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 for use, as triphenylphosphine, tributylphosphine etc.; Can also select quaternary ammonium salt or fluoroborate etc. for use.
6, contain nitrogen combustion inhibitor
Can adopt the existing various nitrogen combustion inhibitor that contains, wherein select nitrogen content to contain nitrogen combustion inhibitor in 15-30 quality % scope, preferred nitrogen content contains nitrogen combustion inhibitor in 15-25 quality % scope.The preferred nitrogenous polyphosphate compound of the present invention, for example: trimeric cyanamide polyphosphate (MPP), piperazine polyphosphate or their mixture.Concrete example has melamine pyrophosphate, trimeric cyanamide triphosphate, trimeric cyanamide pentaphosphate, piperazine pyrophosphate salt, piperazine triphosphate and piperazine pentaphosphate.
7, phosphonium flame retardant
Phosphonium flame retardant can select to adopt Organophosphorous compounds, as phenolic group Alamos oligopolymer (FP110) etc.; Organophosphonate is as dimethyl methyl phosphonate, diethyl ethylphosphate etc.; And phosphinate, for example alkali-metal phosphinate: phosphonous acid sodium or phosphonous acid potassium etc.
8, mineral filler
The present invention does not have special requirement for restriction to mineral filler, and any filler that is used for conventional flexible copper-clad panel material can use.Especially, consideration from fire-retardant auxiliary effect aspect, can use metal oxide, as one or more the mixture in aluminium hydroxide, magnesium hydroxide, talcum powder, titanium dioxide and silicon dioxide, lime carbonate, zeolite, boron nitride, aluminium nitride, clay and the mica.
9, organic solvent
The organic solvent that uses when the present invention is prepared into tackiness agent can be acetone, butanone, pimelinketone, toluene, dimethylbenzene, N, N-N,N-DIMETHYLACETAMIDE, N, one or more in dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, ethylene glycol monomethyl ether, the propylene glycol monomethyl ether.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.
10, oxidation inhibitor
The used oxidation inhibitor of the present invention is polynary hindered phenol type antioxidant, as antioxidant 1010, phosphite antioxidant 168,626 grades or its mixture
11, electrical insulating film
The present invention does not have special restriction to the electrical insulating film that is used for flexible copper-clad plate, and any thin-film material that is generally used for flexible copper-clad 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 the present invention in more detail as following embodiment, but the present invention never is subjected to the restriction of following embodiment:
Embodiment 1:
Halogen-free epoxy resin STRUKTOLVP 3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: 4.5 quality %) 8 weight parts, ULE241P-K-70 (join secondary Science and Technology Co., Ltd., epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %) 16 weight parts, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 246g/eq) 8 weight parts, GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 2 weight parts; Synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 40 weight parts; Diaminodiphenylsulfone(DDS) 2 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; Contain nitrogen combustion inhibitor trimeric cyanamide polyphosphate (MPP, nitrogen content 18%) 43 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 27 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 weight parts.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine the halogen-free flameproof binder composition, coat-thickness is 13 μ m, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and electrolytic copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Embodiment 2:
Halogen-free epoxy resin STRUKTOLVP 3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: 4.5 quality %) 10 weight parts, ULE241P-K-70 (join secondary Science and Technology Co., Ltd., epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %) 21 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) 2 weight parts; Synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 42 weight parts; Diaminodiphenylsulfone(DDS) 8 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; Contain nitrogen combustion inhibitor trimeric cyanamide polyphosphate (MPP, nitrogen content 18%) 46 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 27 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 weight parts.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 30%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine the halogen-free flameproof binder composition, coat-thickness is 13 μ m, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and rolled copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Embodiment 3:
Halogen-free epoxy resin PN-106 (Jin one chemical industry, epoxy equivalent (weight): 340g/eq, phosphorus content: 2.6 quality %) 4 weight parts, STRUKTOL VP3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: 4.5 quality %) 10 weight parts, ULE241P-K-70 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %) 21 weight parts, KET4131A70 (KOLON, epoxy equivalent (weight): 215.5g/eq) 5 weight parts; Synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 18 weight parts; Thermoplastic resin phenoxy resin (PPO*MX-90, SABIC INNOVATIVE PLASTICS) 25 weight parts; Diaminodiphenylsulfone(DDS) 4.6 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.4 weight part; Contain nitrogen combustion inhibitor trimeric cyanamide polyphosphate (MPP, nitrogen content 18%) 60 weight parts.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 38%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
Be coated on the polyimide film that thickness is 12.5 μ m with the liquid dispersion of coating machine the halogen-free flameproof binder composition, coat-thickness is 13 μ m, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and electrolytic copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Embodiment 4:
Halogen-free epoxy resin PN-106 (Jin one chemical industry, epoxy equivalent (weight): 340g/eq, phosphorus content: 2.6 quality %) 4 weight parts, STRUKTOL VP3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: 4.5 quality %) 10 weight parts, ULE241P-K-70 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %) 21 weight parts, KET4131A70 (KOLON, epoxy equivalent (weight): 215.5g/eq) 5 weight parts; Synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 30 weight parts; Thermoplastic resin phenoxy resin (PPO*MX-90, SABIC INNOVATIVE PLASTICS) 10 weight parts; Diaminodiphenylsulfone(DDS) 5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; Nitrogenous fire-retartant agent MP P46 weight part; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 27 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 1.0 weight parts.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 40%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
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, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and electrolytic copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Embodiment 5:
Halogen-free epoxy resin STRUKTOL VP3742 (Meizuishi Firm, epoxy equivalent (weight): 370g/eq, phosphorus content: 4.5 quality %) 10 weight parts, ULE241P-K-70 (join secondary Science and Technology Co., Ltd., epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %) 21 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) 2 weight parts; Synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 46 weight parts; Diaminodiphenylsulfone(DDS) 6 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; Nitrogenous fire-retartant agent MP P 35 weight parts; OP935 (Clariant Produkte GmbH, median size is 1-5 μ m) 9 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 27 weight parts; Antioxidant 1010 (CIBA GEIGYCo., Ltd.) 1.0 weight parts.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
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, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and electrolytic copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Comparative Examples 1:
Halogen-free epoxy resin STRUKTOLVP 3742 (Meizuishi Firm, epoxy equivalent (weight): 370ag/eq, phosphorus content: 4.5 quality %) 10 weight parts, ULE241P-K-70 (join secondary Science and Technology Co., Ltd., epoxy equivalent (weight): 416g/eq, phosphorus content: 2.4 quality %) 21 weight parts, XD-1000 (Nippon Kayaku Co., Ltd epoxy equivalent (weight): 246g/eq) 10 weight parts, synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 40 weight parts; Diaminodiphenylsulfone(DDS) 5.5 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.3 weight part; Nitrogenous fire-retartant agent MP P 18 weight parts; Phosphonium flame retardant OP935 (Clariant Produkte GmbH, median size is 1-5 μ m) 18 weight parts; Aluminium hydroxide (median size 0.8-1.2 μ m, purity is more than 99%) 24 weight parts; Antioxidant 1010 (CIBA GEIGY Co., Ltd.) 0.9 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 35%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
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, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and electrolytic copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Comparative Examples 2:
Halogen-free epoxy resin PN-106 (Jin one chemical industry, epoxy equivalent (weight): 340g/eq, phosphorus content: 2.6 quality %) 4 weight parts, ULE241P-K-70 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 416g/eq, phosphorus content: 20 weight parts, 901 (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 215.5g/eq) 5 weight parts 2.4 quality %); GELR128E (HongChang Electronic Materials Co., Ltd, epoxy equivalent (weight): 185g/eq) 2 weight parts; Synthetic rubber 1072CG (Nantex Industry Co., Ltd. acrylonitrile content 27 quality %) 40 weight parts; Diaminodiphenylsulfone(DDS) 4.6 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.4 weight part; Phosphonium flame retardant OP93560 weight part.Said components is placed sand mill, add butanone solvent, the solids content of regulating composition is 38%, carries out the liquid dispersion that mixed grinding is made the halogen-free flameproof binder composition then.
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, in the forced ventilation baking oven, coated coating is descended dry 5 minutes at 150 ℃ then, thereby make halogen-free flameproof binder composition coating change the glue-line of semi-cured state into.A surface that polyimide film is had the surface of glue-line and electrolytic copper foil (thickness is 18 μ m) uses the roll-type laminating machinees to be bonded together by heat pressure adhesive down at 120 ℃, to be laminated with thing then and put the curing that under 60-180 ℃, heats up in the baking oven into, make flexible copper-clad plate.
Below the performance of the flexible copper-clad plate of the foregoing description and Comparative Examples gained is measured contrast, gained the results are shown in Table one:
1, measuring method:
Flame retardant resistance:
Carve processing flexible copper-clad 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 " * " 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 flexible copper-clad plate is the circuit of 1mm, 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 then, and with this observed value as stripping strength.
Coating strength of joint and zonation test test (MOT test)
Test according to ASTMD5423 (1993), with after the etching for the circuit of 1mm was placed in 150 ℃ the air circulating oven after 240 hours, the bounding force of cool to room temperature test Copper Foil and base material.UL79626C requires stripping strength greater than 0.35Kgf/cm.
Table one
As shown in Table 1, the composition of embodiment 1 to embodiment 5 preparation satisfies demand of the present invention, flexible copper-clad panel material with nitrogenous flame retardant resin composition production demonstrates good stripping strength (normality and MOT), welding thermotolerance and flame retardant resistance, and not halogen-containing, have important prospects for commercial application.And use the phosphorated fire retardant to replace containing nitrogen combustion inhibitor in Comparative Examples 1 and 2, and when comparing with the flexible copper-clad plate that satisfies demand of the present invention, the flexible copper-clad panel material of its gained is at fire-retardant and stripping strength poor-performings such as (MOT).
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 did.
Claims (10)
1. a halogen-free flame-retardant adhesive composition is characterized in that, it comprises the component of following weight part:
15～45 parts of halogen Resins, epoxy
15～60 parts of thermoplastic resin and/or synthetic rubber
0.1～8 part in solidifying agent
Contain 5～60 parts of nitrogen combustion inhibitors.
2. halogen-free flame-retardant adhesive composition according to claim 1, it is characterized in that, when described thermoplastic resin and synthetic rubber mixing use, it is 10-30 part that described thermoplastic resin accounts for weight part, and it is 10-30 part that described synthetic rubber accounts for weight part.
3. halogen-free flame-retardant adhesive composition according to claim 1 and 2, it is characterized in that described halogen Resins, epoxy is the halogen Resins, epoxy of phenol type, biphenyl type, bisphenol A epoxide resin or bisphenol F epoxy resin 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 the acrylonitrile butadiene copolymer of acrylonitrile content between 5-60 quality %; Described solidifying agent adopts based on the solidifying agent of polyamines and/or the solidifying agent of acid anhydride-based; The described nitrogen combustion inhibitor requirement nitrogen content that contains is in 15-30 quality % scope.
4. halogen-free flame-retardant adhesive composition according to claim 3 is characterized in that, the combination of one or more among described synthetic rubber employing Nipol 1072,1072CG and the XER-32; Described solidifying agent based on polyamines adopts one or more the combination in diaminodiphenylsulfone(DDS), phenylenediamine and the diaminodiphenyl-methane; One or more combination in solidifying agent employing Tetra hydro Phthalic anhydride, pyromellitic acid acid anhydride and the hexahydrophthalic anhydride of described acid anhydride-based; The described nitrogen combustion inhibitor that contains adopts trimeric cyanamide, trimeric cyanamide urate, trimeric cyanamide polyphosphate, piperazine polyphosphate, melamine pyrophosphate, trimeric cyanamide triphosphate, trimeric cyanamide pentaphosphate, the melamine salt of tetramethylolmethane phosphate ester acid, piperazine pyrophosphate salt, piperazine triphosphate, piperazine pentaphosphate and 2; 4-diamino-6-diethoxy phosphoryl-1; 3, the combination of one or more in the 5-triazine.
5. halogen-free flame-retardant adhesive composition according to claim 4 is characterized in that it also comprises mineral filler, and described mineral filler consumption is 5-60 part.
6. halogen-free flame-retardant adhesive composition according to claim 5 is characterized in that it also comprises solidifying agent promotor, and described solidifying agent accelerator level is 0.1-1 part.
7. halogen-free flame-retardant adhesive composition according to claim 6 is characterized in that, described solidifying agent promotor is adopted one or more mixing in imidazolium compounds, three organic phosphine compounds, quaternary ammonium salt and the fluoroborate.
8. halogen-free flame-retardant adhesive composition according to claim 7 is characterized in that it also comprises phosphonium flame retardant, and described phosphonium flame retardant addition is 5-15 part.
9. halogen-free flame-retardant adhesive composition according to claim 8 is characterized in that, it also comprises 0.1-3 part oxidation inhibitor.
10. flexible copper-clad plate, it has electrical insulating film, bonding coat and Copper Foil, and described bonding coat is formed by the described halogen-free flame-retardant adhesive preparation of compositions of the arbitrary claim of claim 1～9.
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Address after: 528400 Zhongshan Torch Development Zone, science and technology Avenue, along the River Road, Guangdong Patentee after: ZHONGSHAN ALLSTAR ELECTRONIC MATERIALS CO., LTD. Address before: 528437 Yanjiang Road, science and technology Avenue, Torch Development Zone, Zhongshan, Guangdong Patentee before: Allstar Electronic Material (Zhongshan) Co., Ltd. |