CN101851390A - Black halogen-free epoxy resin composition and covering film prepared from same - Google Patents
Black halogen-free epoxy resin composition and covering film prepared from same Download PDFInfo
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- CN101851390A CN101851390A CN 201010177757 CN201010177757A CN101851390A CN 101851390 A CN101851390 A CN 101851390A CN 201010177757 CN201010177757 CN 201010177757 CN 201010177757 A CN201010177757 A CN 201010177757A CN 101851390 A CN101851390 A CN 101851390A
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Abstract
The invention relates to a black halogen-free epoxy resin composition and a covering film prepared from the same. The black halogen-free epoxy resin composition comprises epoxy resin, CTBR (Carboxyl Terminated Butadiene Rubber), acrylic ester modified epoxy resin, a curing agent, a curing accelerator, carbon black powder, titanium dioxide, a phosphorus flame retardant, inorganic fillers and an organic solvent. The covering film prepared from the composition comprises a polyimide insulated film, a black halogen-free epoxy resin composition coating coated on the polyimide insulated film and release paper covered on the black halogen-free epoxy resin composition coating. The resin composition does not contain halogens, is black by adopting less carbon black powder to play the shading effect and adopts titanium dioxide to enhance the shading effect. Meanwhile, the acrylic ester modified epoxy resin is used so that a resin system reaches fire retardance and keeps favorable mechanical performance. The covering film prepared from the composition reaches the standards of surface resistance and volume resistivity, reaches a flame retardance level of UL 94 V-0 and has high peeling strength and excellent size stability, flexibility and processing performance.
Description
Technical field
The present invention relates to a kind of halogen-free epoxy resin composition, the mulch film that relates in particular to a kind of black halogen-free epoxy resin composition and use its preparation.
Background technology
The mulch film of flexible printed circuit (FPCB) usefulness not only plays the welding resistance effect, and makes FPCB not be subjected to the erosion of dust, moisture, pharmaceutical chemicals and reduce stress influence in the BENDING PROCESS.Mulch film is to apply one deck tackiness agent on polyimide (PI) film, and baking desolventizes then, is composited with separate-type paper again.Usually used tackiness agent has epoxy resin, acrylic ester, polyester system etc., open 2004-137437, WO2008/136096, CN 1847352A, CN 1670107A etc. as the spy, wherein mainly contain two kinds of acrylic ester and epoxy resin, both respectively have quality, the mulch film shelf lives of acrylic ester is long, cementability good, but thermotolerance is relatively poor; The excellent heat resistance of epoxy resin, but the shelf lives is shorter, and two kinds of parallel development of glue system promote the lifting of mulch film performance jointly.Mulch film is main with halogen flame retardant glue still at present, adopts the very high brominated resins of bromine content to reach fire-retardant purpose, but there is the hidden danger that produces the carcinogenic substance dioxin in product in discarded burning disposal process; And the enforcement of the RoHS of European Union instruction has proposed to contain the requirement of environmental management materials such as lead, mercury, cadmium, sexavalent chrome, Polybrominated biphenyl, Poly Brominated Diphenyl Ethers to electronic product.In order to satisfy the environmental protection trend of " leadless process " and " Halogen material ", each producer is all at active development Halogen product.Sales volume according to Japanese market survey institute JMS prediction halogen-free flame-retardant flexibility coat copper plate and mulch film will be increased to 2010 from 800,000 square metres in 2003 7700000 square metres.The without halide Kapton mulch film of environmental management materials such as not halogen-containing and plumbous, mercury, cadmium, sexavalent chrome faces good opportunity to develop.
Recently, market is more and more stronger to the demand of black mulch film, than common mulch film, its opaque, no reflection events, be mainly used in preparation LED lamp plate, auto lamp etc., backlight owing to not reflecting, therefore this opaque mulch film can strengthen the contrast gradient of luminous source, helps to improve the working efficiency of photoelectric component; In addition, the black mulch film also is widely used in the manufacturing of mobile phone.With regard to the technology of preparing of black mulch film, two kinds of approach are arranged: the one, common mulch film is coated on the black PI film with glue; The 2nd, special a kind of black glue is coated in (as US 2004/0142191) on the common PI film.For batch process, first kind of approach only need be changed starting material, and be easy and simple to handle; Second kind of approach then will be started with from prescription, and brings certain puzzlement to production operation.But there is a problem, the black PI film of the above thickness of 25 μ m all has sale both at home and abroad, and 12.5 μ m only have Du Pont to produce (trade mark is Kapton-CB), for sale hardly, at present some producers are also arranged at the black PI of this specification of active development film, but all not mature enough and cost an arm and a leg, and the client often needs the black mulch film of 12.5 μ mPI films, forcedly only take second kind of technological approaches.The present invention does to set forth with regard to a kind of halogen-free epoxy resin composition of black and with the black mulch film of its preparation.
Summary of the invention
The object of the present invention is to provide a kind of black halogen-free epoxy resin composition, make its blackening and shading, use titanium dioxide to play the enhancing interception simultaneously by adding carbon powder.
Another object of the present invention is to, a kind of mulch film that uses the above-mentioned composition preparation is provided, it possesses excellent opacifying property, insulating property, thermotolerance, covers shape property, cementability and flame retardant resistance.
For achieving the above object, the invention provides a kind of black halogen-free epoxy resin composition, said composition comprises that component and weight part thereof are as follows: Resins, epoxy 30-60 part, nbr carboxyl terminal 20-40 part, acrylate modified Resins, epoxy 5-25 part, solidifying agent 1-10 part (per 100 gram resin and rubber proportions), curing catalyst 0.01-1.0 part, carbon powder 1-6 part, titanium dioxide 1-20 part, phosphonium flame retardant 10-25 part, mineral filler 0-100 part, and solvent an amount of.Wherein, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 30-40% of total weight percent.
Simultaneously, a kind of mulch film that uses the above-mentioned composition preparation is provided, comprise: the polyimide insulative film, be coated on the black halogen-free epoxy resin composition coating on the polyimide insulative film and be laminated with separate-type paper on the black halogen-free epoxy resin composition coating, wherein, the thickness of polyimide insulative film is 10-100 μ m, separate-type paper thickness is 50-150 μ m, and gluing thickness is 10-35 μ m; The dry thickness of black halogen-free epoxy resin composition coating is 5-45 μ m, preferred 10-35 μ m.
Beneficial effect of the present invention: resin combination of the present invention is not halogen-containing, adopts a small amount of carbon powder to make it to become black and has reached interception, adopts titanium dioxide to play the enhancing interception; Use acrylate modified Resins, epoxy simultaneously, make to keep mechanical property preferably when resin system reaches flame retardant resistance.With the black mulch film of said composition preparation, surface resistivity and volume specific resistance are up to standard, and flame retardant resistance reaches the UL94V-0 level, has high-peeling strength, excellent size stability, flexibility and processing characteristics.
Embodiment
Halogen-free epoxy resin composition of the present invention comprises: Resins, epoxy, nbr carboxyl terminal, acrylate modified Resins, epoxy, solidifying agent, curing catalyst, carbon powder, titanium dioxide, phosphonium flame retardant, filler, oxidation inhibitor and organic solvent.
The weight proportion of above-mentioned raw materials (by the listed as parts by weight of constituent) is:
Resins, epoxy 30-60 part;
Nbr carboxyl terminal 20-40 part;
Acrylate modified Resins, epoxy 5-25 part;
Solidifying agent 1-10 part;
Curing catalyst 0.01-1.0 part;
Carbon powder 1-6 part;
Titanium dioxide 1-20 part;
Phosphonium flame retardant 10-25 part;
Filler 0-100 part;
Oxidation inhibitor 0.01-1.0 part;
Organic solvent is an amount of.
Each feedstock detail is as follows:
(1) Resins, epoxy
Above-mentioned Resins, epoxy mainly is some not halogen-containing resins that possess special construction, or has excellent thermotolerance or have special fire retardant mechanism, and requires this resin and nbr carboxyl terminal to possess good consistency.NC-3000, NC-3000-H, NC-2000, XD-1000 that the Resins, epoxy of this class special construction has Nippon Kayaku K. K to make, HP-7200L, the HP-7200, HP-7200H, HP-7200HH, EXA-4816, the EXA-4840 etc. that also have Dainippon Ink. ﹠ Chemicals Inc to make, the Resins, epoxy such as SEN-100, SE-110 that also have star Co., Ltd. of Korea S elder generation to make in addition.
These halogen-free epoxy resins can use separately, perhaps being used in combination with two or more different resins.
(2) nbr carboxyl terminal
Nbr carboxyl terminal is acrylonitrile butadiene copolymer normally, wherein acrylonitrile content can be at 18-50 quality %, preferably at 20-30 quality %, wherein the copolymer molecule chain end is by carboxylated, and the copolymer rubber of vinyl cyanide, divinyl and carboxylic monomer such as vinylformic acid or toxilic acid.The carboxylated of molecule chain end can realize as the monomer of methacrylic acid etc. with comprising carboxyl in the above-mentioned copolymer rubber.The object lesson of these commercially available carboxylic NBR comprises Nipol 1072CG (ZeonCorporation manufacturing) and high purity, hangs down ionic product XER-32 (JSR Corporation manufacturing).
(3) acrylate modified Resins, epoxy
Acrylate modified Resins, epoxy and CTBN is shared, adjustment by curing system, can bring into play two kinds of elastomeric advantages simultaneously, also has a certain amount of small molecules Resins, epoxy in addition in this resin, also can increase the cross-linking density of cured article, improve the cohesive strength of finished product glue-line, help to improve the stripping strength of mulch film.Commercially available acrylate modified Resins, epoxy comprises that (Nippon Shokubai Co., Ltd makes, elastomer content 20 quality % etc. for BPA 328 and BPF 307 at present.
(4) solidifying agent
Solidifying agent adopts amine curing agent, amine curing agent commonly used has 4,4-diaminodiphenylsulfone(DDS) (4,4-DDS), 3, the 3-diaminodiphenylsulfone(DDS) (3,3-DDS), 4,4-diaminodiphenyl oxide, Dyhard RU 100 etc., wherein the temperature of reaction of DDS cured epoxy resin is higher, but can help to improve the thermotolerance of product.
(5) curing catalyst
Above-mentioned curing catalyst is the imidazoles curing catalyst, can be in glyoxal ethyline, 1-Methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, the 2-phenyl-4-methylimidazole one or more.
(6) carbon powder
The present invention mainly uses carbon powder to reach that mulch film turns black and the shading purpose.Carbon powder is divided into graphitized carbon black and colour carbon black, in order to guarantee the insulating property of product, can only adopt colour carbon black.Commercially available colour carbon black powder has 2808 (the refreshing painted sculptures glue of Dongguan City Products Co., Ltd makes), HI-Black 50L (Korea S KCB manufacturing) etc.
Carbon powder is one of black pigment of using always, and the present invention uses colour carbon black, and selection blackness height, the thermally oxidized black that particle diameter is little are advisable, and coordinate the blackness of composition epoxy resin and the contradiction between the insulating property to the full extent; In addition, carbon black is one of the most difficult dispersive pigment, whether is distributed to the micropartical state that meets optical property and directly has influence on sooty blackness, form and aspect and covering power.Comprehensive blackness and insulating property, the carbon black usage quantity is the best with the 3-5 weight part.
(7) titanium dioxide
Titanium dioxide possesses very strong refractive power effect, adds to make that on a small quantity mulch film can printing opacity, strengthens the contrast gradient of light source effectively.Commodity have two kinds: a kind of is rutile titanium dioxide, proportion 4.26, and refractive index 2.72, photostabilization is very strong, is applicable to exterior product; A kind of is anatase titanium dioxide, and thermotolerance is poor slightly, and easily yellowing, not weather resistance are suitable for indoor product.In order to improve reliability of products and weathering resistance, adopt the titanium dioxide of rutile-type, commercially available product has R-706, R-7060, R-900, R-902, R-960 (Du Pont's manufacturing) etc.
Though titanium dioxide possesses very strong shaded effect, itself is white in color, if addition is little, may not reach the shading requirement; If addition is big, then can offset the blackness of the composition epoxy resin that carbon black brings, present brown even grey, so the usage quantity of titanium dioxide will be weighed colourity and shaded effect and decide.Take all factors into consideration shaded effect and blackness, the titanium dioxide usage quantity is the best with the 5-15 weight part.
(8) phosphonium flame retardant
Phosphonium flame retardant commonly used has SPB-100 (manufacturings of Ri Ben Otsuka Chemical Co., Ltd), OP-935 (German Clariant company make), SP-703H (four countries change into Co., Ltd.'s manufacturing) etc.Whether except considering flame retarding efficiency, whether influencing the glue amount of overflowing, whether influencing the shelf lives, be heated to surface transport etc. for a long time all is the factor that must consider when being used to prepare mulch film.
(9) filler
Above-mentioned filler is mineral filler, can be aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, lime carbonate, clay, boehmite, talcum and mica etc., uses one or more mixture wherein.
(10) oxidation inhibitor
The main purpose of oxidation inhibitor in resin combination is to reduce Resins, epoxy and the oxidation situation of acrylonitrile-butadiene rubber in hot setting and following process process.Employed oxidation inhibitor can be 1010,1222,1076 (CIBA GEIGY Co. manufacturings) and 399,312,210 (GE Specially Chemicals manufacturings) etc., and home-made oxidation inhibitor such as commodity are called DNP (production of the triumphant source of Qujiang District, Quzhou City, Zhejiang Fine Chemical Works) etc.More than the oxidation inhibitor of these different names of an article can optionally select for use a kind of separately or mix two or more uses.The interpolation scope that oxidation inhibitor is formed at composition is the 0.01-1.0 weight part.
(11) organic solvent
Above-mentioned organic solvent can be one or more in acetone, butanone, pimelinketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ethyl acetate etc.In the composition of preparation, the preferred 30-40 weight of amount of solid content %, the viscosity that can obtain to suit provides good workability, guarantees not occur in coating procedure visual defects.
Use similar devices such as ball mill, jar mill, sand mill, and be used high-shear dispersed with stirring equipment, the inoganic solids component and the organic solvent of organic solid component in the present composition and interpolation can be mixed.
Above-mentioned composition can be used for the preparation of mulch film.Utilize organic solvent to mix the black liquid state dispersion that required component forms the present composition, use coating equipment that this dispersion is coated on the polyimide insulative film.Make the insulating film that is coated with dispersion through online drying oven, 80-160 ℃ of heating 2 to 8 minutes, remove organic solvent and drying composition thus, contain the said composition layer of semicure attitude with formation, next 80-100 ℃ down and separate-type paper compound, rolling promptly obtains the black mulch film.
The dry thickness of composition coating film is 5-45 μ m in the above-mentioned mulch film, preferred 10-35 μ m.
The thickness of above-mentioned used polyimide insulative film is 10-100 μ m, and separate-type paper thickness is 50-150 μ m, and gluing thickness is 10-35 μ m.
Observe its color and luster and light transmission at the above-mentioned black mulch film of making, test its excessive glue amount, thermotolerance, flame retardant resistance and stripping strength, further give to illustrate in detail and describe as following embodiment.
Now the embodiment of the invention is described in detail as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
Resins, epoxy (marque NC-3000-H, epoxy equivalent (weight) 290g/eq, Japanese chemical drug manufacturing) 35 weight parts; Nbr carboxyl terminal (Zeon Corporation makes for marque Nipol 1072CG, acrylonitrile content 27 quality %) 21 weight parts; Acrylate modified Resins, epoxy (Nippon Shokubai Co., Ltd makes for marque BPF307, elastomer content 20 quality %) 9.1 weight parts; Diaminodiphenylsulfone(DDS) (DDS) 6.63 weight parts; 1-cyanoethyl-2-ethyl-4-methylimidazole (2E4MZ-CN) 0.163 weight part; Carbon powder (marque HI-Black 50L, Korea S KCB makes) 1.95 weight parts; Titanium dioxide (marque R-706, Du Pont makes) 6.5 weight parts; Phosphonium flame retardant (marque OP-935, German Clariant manufacturing) 13 weight parts; Oxidation inhibitor (marque 1010, CIBA GEIGY Co. makes) 0.05 weight part.The solids content of regulating glue with butanone solvent is 38%, mixes and makes black halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m by spreadometer, gluing thickness is 15 μ m, put in 160 ℃ the baking oven heating again into 3 minutes, on the polyimide insulative film, to form partly solidified composition layer, then itself and separate-type paper are laminated with by roll-in, rolling obtains the mulch film of black.
Embodiment 2: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 4.0 parts of carbon powders, 5.0 parts of titanium dioxide.
Embodiment 3: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 4.0 parts of carbon powders, 10.0 parts of titanium dioxide.
Embodiment 4: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 5.0 parts of carbon powders, 5.0 parts of titanium dioxide.
Embodiment 5: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 5.0 parts of carbon powders, 10.0 parts of titanium dioxide.
Comparative example 1: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 1.0 parts of carbon powders, 15.0 parts of titanium dioxide.
Comparative example 2: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 1.0 parts of carbon powders, 20.0 parts of titanium dioxide.
Comparative example 3: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 2.0 parts of carbon powders, 10.0 parts of titanium dioxide.
Comparative example 4: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 2.0 parts of carbon powders, 15.0 parts of titanium dioxide.
Comparative example 5: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium dioxide, other component adding proportions are identical.Add 6.0 parts of carbon powders, 5.0 parts of titanium dioxide.
Specifically see the following form:
The performance of the formulation Example of table 1. halogen-free epoxy resin composition and the flexibility coat copper plate of preparation thereof
The performance of the prescription comparative example of table 2. halogen-free epoxy resin composition and the flexibility coat copper plate of preparation thereof
The testing method of above characteristic is as follows:
(1) testing method of printing opacity: with sample facing to high light, visual whether printing opacity.
(2) surface resistivity and volume specific resistance after damp and hot are tested according to IPC-TM-650 2.5.17 method.
(3) excessive glue amount is tested according to IPC-TM-650 2.3.17.1 method.
(4) stripping strength (PS) is tested the stripping strength of crown cap according to IPC-TM-650 2.4.9 method.
(5) anti-immersed solder is tested according to IPC-TM-650 2.4.13.
(6) incendivity (flame retardant resistance): measure according to UL 94 vertical combustion methods.
In sum, resin combination of the present invention is not halogen-containing, adopts a small amount of carbon powder to make it to become black and has reached interception, adopts titanium dioxide to play the enhancing interception; Use acrylate modified Resins, epoxy simultaneously, make to keep mechanical property preferably when resin system reaches flame retardant resistance.With the black mulch film of said composition preparation, surface resistivity and volume specific resistance are up to standard, and flame retardant resistance reaches UL94 V-0 level, has high-peeling strength, excellent size stability, flexibility and processing characteristics.
The above; it only is preferred embodiment of the present invention; for the person of ordinary skill of the art, can make other various corresponding changes and distortion, and all these changes and distortion all should belong to the protection domain of claim of the present invention according to technical scheme of the present invention and technical conceive.
Claims (9)
1. black halogen-free epoxy resin composition, it is characterized in that, comprise that component and weight part thereof are as follows: Resins, epoxy 30-60 part, nbr carboxyl terminal 20-40 part, acrylate modified Resins, epoxy 5-25 part, solidifying agent 1-10 part, curing catalyst 0.01-1.0 part, carbon powder 1-6 part, titanium dioxide 1-20 part, phosphonium flame retardant 10-25 part, mineral filler 0-100 part, and organic solvent an amount of; Wherein, solid ingredient is dissolved in organic solvent, and solid ingredient accounts for the 30-40% of total weight percent.
2. black halogen-free epoxy resin composition as claimed in claim 1, it is characterized in that, described nbr carboxyl terminal is an acrylonitrile butadiene copolymer, wherein acrylonitrile content is 18-50 quality %, the copolymer molecule chain end is by carboxylated, and vinyl cyanide, divinyl and carboxylic monomeric copolymer rubber.
3. black halogen-free epoxy resin composition as claimed in claim 1 is characterized in that, described solidifying agent is an amine curing agent, adopts 4,4-diaminodiphenylsulfone(DDS), 3,3-diaminodiphenylsulfone(DDS), 4,4-diaminodiphenyl oxide or Dyhard RU 100.
4. black halogen-free epoxy resin composition as claimed in claim 1, it is characterized in that, described curing catalyst is the imidazoles curing catalyst, is in glyoxal ethyline, 1-Methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecyl imidazole, the 2-phenyl-4-methylimidazole one or more.
5. black halogen-free epoxy resin composition as claimed in claim 1 is characterized in that, described carbon powder adopts colour carbon black, and titanium dioxide adopts the titanium dioxide of rutile-type.
6. non-halogen non-phosphate composition epoxy resin as claimed in claim 1, it is characterized in that the mixture of one or more in described mineral filler employing aluminium hydroxide, magnesium hydroxide, zeolite, wollastonite, silicon-dioxide, magnesium oxide, Calucium Silicate powder, lime carbonate, clay, boehmite, talcum and the mica.
7. non-halogen non-phosphate composition epoxy resin as claimed in claim 1 is characterized in that, described organic solvent is one or more in acetone, butanone, pimelinketone, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ethyl acetate.
8. mulch film that uses black halogen-free epoxy resin composition preparation as claimed in claim 1, it is characterized in that, comprise: the polyimide insulative film, be coated on the black halogen-free epoxy resin composition coating on the polyimide insulative film and be laminated with separate-type paper on the black halogen-free epoxy resin composition coating, wherein, the thickness of polyimide insulative film is 10-100 μ m, separate-type paper thickness is 50-150 μ m, and gluing thickness is 10-35 μ m; The dry thickness of black halogen-free epoxy resin composition coating is 5-45 μ m.
9. mulch film as claimed in claim 8 is characterized in that, the dry thickness of black halogen-free epoxy resin composition coating is 10-35 μ m.
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