CN101851390B - 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
- Publication number
- CN101851390B CN101851390B CN201010177757XA CN201010177757A CN101851390B CN 101851390 B CN101851390 B CN 101851390B CN 201010177757X A CN201010177757X A CN 201010177757XA CN 201010177757 A CN201010177757 A CN 201010177757A CN 101851390 B CN101851390 B CN 101851390B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- resin composition
- black
- free epoxy
- halogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
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 resistance weldering effect, and makes FPCB not receive the erosion of dust, moisture, pharmaceutical chemicals and reduce stress influence in the BENDING PROCESS.Mulch film is on polyimide (PI) film, to apply one deck tackiness agent, 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. like the spy; Wherein mainly contain two kinds of acrylic ester and epoxy resin; Both respectively have quality, and 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 system still at present, adopt 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, PBBs, PBDE 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.Absatzvolumen 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, and 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 photogen, 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 (like US 2004/0142191) on the common PI film.As far as 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), and is 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 oxide to play the enhancing interception simultaneously through adding carbon powder.
Another object of the present invention is to, a kind of mulch film that uses the above-mentioned compsn preparation is provided, it possesses excellent opacifying property, insulating property, thermotolerance, covers shape property, cementability and flame retardant resistance.
For realizing above-mentioned purpose; The present invention provides a kind of black halogen-free epoxy resin composition, and said composition comprises that component and weight part thereof are following: epoxy resin 30-60 part, nbr carboxyl terminal 20-40 part, acrylate modified epoxy resin 5-25 part, solidifying agent 1-10 part (per 100 gram resins and rubber proportions), curing catalyst 0.01-1.0 part, carbon powder 1-6 part, titanium oxide 1-20 part, phosphonium flame retardant 10-25 part, mineral filler 0-100 part, to reach 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 compsn 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 the 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 oxide to play the enhancing interception; Use acrylate modified epoxy resin 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, have high-peeling strength, excellent size stability, flexibility and processing characteristics.
Embodiment
Halogen-free epoxy resin composition of the present invention comprises: epoxy resin, nbr carboxyl terminal, acrylate modified epoxy resin, solidifying agent, curing catalyst, carbon powder, titanium oxide, 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:
Epoxy resin 30-60 part;
Nbr carboxyl terminal 20-40 part;
Acrylate modified epoxy resin 5-25 part;
Solidifying agent 1-10 part;
Curing catalyst 0.01-1.0 part;
Carbon powder 1-6 part;
Titanium oxide 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 following:
(1) epoxy resin
Above-mentioned epoxy resin 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 epoxy resin of this type special construction has Nippon Kayaku K. K to make; Also have HP-7200L that Dainippon Ink. & Chemicals Inc makes, HP-7200, HP-7200H, HP-7200HH, EXA-4816, EXA-4840 etc., also have epoxy resin such as SEN-100 that star Co., Ltd. of Korea S elder generation makes, SE-110 in addition.
These halogen-free epoxy resins can use separately, perhaps use with the combination of 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 like the monomer of methylacrylic 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 epoxy resin
Acrylate modified epoxy resin and CTBN is shared; Adjustment through curing system; Can bring into play two kinds of elastomeric advantages simultaneously, also have a certain amount of small molecules epoxy resin 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 epoxy resin comprises that (Nippon Shokubai Co., Ltd makes BPA 328, elastomer content 20 quality % etc. with BPF 307 at present.
(4) solidifying agent
Solidifying agent adopts amine curing agent, and 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, selects the thermally oxidized black that blackness is high, particle diameter is little to be advisable, and coordinates 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 oxide
Titanium oxide 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, is prone to yellowing, not weather resistance, is suitable for indoor product.In order to improve reliability of products and weathering resistance, adopt the titanium oxide of rutile-type, commercially available product has R-706, R-7060, R-900, R-902, R-960 (Du Pont's manufacturing) etc.
Though titanium oxide possesses very strong shaded effect, itself is white in color, if addition is little, possibly 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 oxide will be weighed colourity and shaded effect and decide.Take all factors into consideration shaded effect and blackness, the titanium oxide usage quantity is the best with the 5-15 weight part.
(8) phosphonium flame retardant
Phosphonium flame retardant commonly used has SPB-100 (manufacturing of Ri Ben Otsuka Chemical Co., Ltd), OP-935 (German Clariant manufactured), SP-703H (four countries change into Co., Ltd. and make) 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 white lake, Marinco H, zeolite, wollastonite, silicon-dioxide, Natural manganese dioxide, 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 epoxy resin 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 compsn is the 0.01-1.0 weight part.
(11) organic solvent
Above-mentioned organic solvent can be one or more in acetone, butanone, pimelinketone, EGME, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ETHYLE ACETATE etc.In the compsn of preparation, the preferred 30-40 weight of amount of solid content %, the viscosity that can obtain to suit provides good workability, guarantees in coating procedure, not occur visual defects.
Use similar devices such as ball mill, jar mill, sand mill, and be used high-shear dispersed with stirring equipment, can the inoganic solids component and the organic solvent of organic solid component in the present composition and interpolation be mixed.
Above-mentioned compsn can be used for the preparation of mulch film.Utilize organic solvent to mix the black liquid state dispersion-s that required component forms the present composition, use coating equipment that this dispersion-s is coated on the polyimide insulative film.Make the insulating film that is coated with dispersion-s through online drying oven; 80-160 ℃ of heating 2 to 8 minutes, remove organic solvent and drying compsn 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 to the above-mentioned black mulch film of processing, test its excessive glue amount, thermotolerance, flame retardant resistance and stripping strength, further give to explain in detail and describe like following embodiment.
Now the embodiment of the invention is specified as follows, but the present invention is confined to scope of embodiments.
Embodiment 1:
Epoxy resin (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 epoxy resin (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 oxide (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 using butanone solvent to regulate glue is 38%, mixes and processes black halogen-free epoxy resin composition.Be coated in said composition on the polyimide insulative film of thickness 12.5 μ m through 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 through 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 oxide, other component adding proportions are identical.Add 4.0 parts of carbon powders, 5.0 parts of titanium oxide.
Embodiment 3: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 4.0 parts of carbon powders, 10.0 parts of titanium oxide.
Embodiment 4: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 5.0 parts of carbon powders, 5.0 parts of titanium oxide.
Embodiment 5: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 5.0 parts of carbon powders, 10.0 parts of titanium oxide.
Comparative example 1: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 1.0 parts of carbon powders, 15.0 parts of titanium oxide.
Comparative example 2: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 1.0 parts of carbon powders, 20.0 parts of titanium oxide.
Comparative example 3: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 2.0 parts of carbon powders, 10.0 parts of titanium oxide.
Comparative example 4: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 2.0 parts of carbon powders, 15.0 parts of titanium oxide.
Comparative example 5: benchmark prescription amount of solid is by 100 listed as parts by weight, and except that carbon powder and titanium oxide, other component adding proportions are identical.Add 6.0 parts of carbon powders, 5.0 parts of titanium oxide.
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 following:
(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 property 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 oxide to play the enhancing interception; Use acrylate modified epoxy resin 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, have high-peeling strength, excellent size stability, flexibility and processing characteristics.
The above; Be merely 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 (6)
1. the mulch film of black halogen-free epoxy resin composition preparation; 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 the 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;
Said black halogen-free epoxy resin composition comprises that component and weight part thereof are following: epoxy resin 30-60 part, nbr carboxyl terminal 20-40 part, acrylate modified epoxy resin 5-25 part, solidifying agent 1-10 part, curing catalyst 0.01-1.0 part, carbon powder 1-6 part, titanium oxide 5-15 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; Said solidifying agent is an amine curing agent, adopts 4,4-diaminodiphenylsulfone(DDS), 3,3-diaminodiphenylsulfone(DDS), 4,4-diaminodiphenyl oxide or Dyhard RU 100; Said carbon powder adopts colour carbon black, and titanium oxide adopts the titanium oxide of rutile-type.
2. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1 is characterized in that the dry thickness of black halogen-free epoxy resin composition coating is 10-35 μ m.
3. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that; Said nbr carboxyl terminal is an acrylonitrile butadiene copolymer; Wherein acrylonitrile content is 18-50 quality %, and the copolymer molecule chain end is by carboxylated, and vinyl cyanide, divinyl and carboxylic monomeric copolymer rubber.
4. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that; Said 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. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that the mixture of one or more in said mineral filler employing white lake, Marinco H, zeolite, wollastonite, silicon-dioxide, Natural manganese dioxide, Calucium Silicate powder, lime carbonate, clay, boehmite, talcum and the mica.
6. the mulch film of black halogen-free epoxy resin composition preparation as claimed in claim 1; It is characterized in that said organic solvent is one or more in acetone, butanone, pimelinketone, EGME, propylene glycol monomethyl ether, 1-Methoxy-2-propyl acetate, the ETHYLE ACETATE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010177757XA CN101851390B (en) | 2010-05-19 | 2010-05-19 | Black halogen-free epoxy resin composition and covering film prepared from same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010177757XA CN101851390B (en) | 2010-05-19 | 2010-05-19 | Black halogen-free epoxy resin composition and covering film prepared from same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101851390A CN101851390A (en) | 2010-10-06 |
| CN101851390B true CN101851390B (en) | 2012-05-23 |
Family
ID=42803080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010177757XA Expired - Fee Related CN101851390B (en) | 2010-05-19 | 2010-05-19 | Black halogen-free epoxy resin composition and covering film prepared from same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101851390B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311613B (en) * | 2011-04-03 | 2013-09-18 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and adhesive film prepared from same |
| CN102304272B (en) * | 2011-04-03 | 2013-08-14 | 广东生益科技股份有限公司 | Black halogen-free flame-retardant epoxy resin composition and cover film prepared from same |
| CN103101265A (en) * | 2011-11-11 | 2013-05-15 | 松扬电子材料(昆山)有限公司 | Colored cover film |
| CN102529262B (en) * | 2011-12-30 | 2014-07-16 | 常熟市富邦胶带有限责任公司 | High temperature resistant coating-type black matt polyimide film |
| CN102731743B (en) * | 2012-06-26 | 2014-05-07 | 华烁科技股份有限公司 | Preparation of white thermosetting resin used for LED light having encapsulating film |
| CN103525086B (en) * | 2012-07-04 | 2015-12-16 | 合正科技股份有限公司 | High heat-resisting, low rigidity, nonflammable resin and composition thereof |
| CN103483586B (en) * | 2013-09-25 | 2016-04-06 | 广东生益科技股份有限公司 | Modified polyimide resin, the Adhesive composition containing this modified polyimide resin and the mulch film containing this Adhesive composition |
| CN103554844B (en) | 2013-10-29 | 2016-02-17 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and uses thereof |
| CN106221613A (en) * | 2016-08-30 | 2016-12-14 | 广东永创鑫电子有限公司 | A kind of glue for many colors coverlay and preparation method thereof |
| CN106398654A (en) * | 2016-08-30 | 2017-02-15 | 广东永创鑫电子有限公司 | Heat conduction material for LED (light-emitting diode) flexible circuit board and preparation method of heat conduction material |
| CN106398590A (en) * | 2016-09-13 | 2017-02-15 | 深圳市海纳泰兴电子有限公司 | Halogen-free cover film adhesion agent |
| CN107619643A (en) * | 2017-10-13 | 2018-01-23 | 苏州赛伍应用技术股份有限公司 | Photovoltaic module busbar insulating tape, busbar and photovoltaic module comprising the insulating tape |
| CN109554149B (en) * | 2018-10-18 | 2021-04-27 | 哈尔滨工业大学无锡新材料研究院 | Epoxy adhesive for flexible circuit board and preparation method and application thereof |
| CN110305445A (en) * | 2019-05-16 | 2019-10-08 | 浙江华正新材料股份有限公司 | A kind of black-colored resin composition, prepreg and laminate |
| CN113844130A (en) * | 2021-09-13 | 2021-12-28 | 山东金宝电子股份有限公司 | Preparation method of high-Tg high-frequency copper-clad plate |
| CN115926576A (en) * | 2022-12-13 | 2023-04-07 | 东莞市毅联电子科技有限公司 | Shading coating for flexible circuit board and preparation method and use method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637595A (en) * | 2003-12-24 | 2005-07-13 | 罗姆和哈斯电子材料有限责任公司 | Mask |
| CN101280093A (en) * | 2008-05-13 | 2008-10-08 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate |
| CN101526734A (en) * | 2008-03-07 | 2009-09-09 | 富士胶片株式会社 | Photo mask material, photo mask and photo mask preparing method |
-
2010
- 2010-05-19 CN CN201010177757XA patent/CN101851390B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1637595A (en) * | 2003-12-24 | 2005-07-13 | 罗姆和哈斯电子材料有限责任公司 | Mask |
| CN101526734A (en) * | 2008-03-07 | 2009-09-09 | 富士胶片株式会社 | Photo mask material, photo mask and photo mask preparing method |
| CN101280093A (en) * | 2008-05-13 | 2008-10-08 | 广东生益科技股份有限公司 | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101851390A (en) | 2010-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101851390B (en) | Black halogen-free epoxy resin composition and covering film prepared from same | |
| CN102101935B (en) | Halogen-free epoxy resin composition and flexible copper clad plate prepared from same | |
| TWI541286B (en) | A white thermosetting resin composition, and a printed circuit board having the cured product or a reflective plate for a light-emitting element | |
| CN102127291B (en) | Halogen-free epoxy resin composition and covering film prepared from same | |
| CN102127290B (en) | Epoxy resin composition and flexible copper-clad plate prepared from same | |
| CN101633770B (en) | Halogen-free flame retardant epoxy resin composite and flexible copper clad laminate prepared with same | |
| CN102010569B (en) | Halogen-free flame retardant epoxy resin composition and high-flexibility coating film prepared by same | |
| CN101280093B (en) | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate | |
| CN102311613B (en) | Black halogen-free flame-retardant epoxy resin composition and adhesive film prepared from same | |
| CN106280698B (en) | High-temperature-resistant PI white label ink and preparation method thereof | |
| CN102093667B (en) | Epoxy resin composite and covering film prepared from same | |
| KR20130069336A (en) | Delustrant composed of polyimide powder, polyimide film incorporating the delustrant, and manufacture thereof | |
| KR20080014830A (en) | White prepreg, white laminated plate, and metal foil clad white laminated plate | |
| CN104419013A (en) | Colored polyimide film | |
| CN102010578A (en) | Black halogen free resin composite, cover film prepared by using same and making method thereof | |
| CN102304272B (en) | Black halogen-free flame-retardant epoxy resin composition and cover film prepared from same | |
| CN104629342A (en) | Resin composition and covering film prepared from resin composition | |
| CN101831144B (en) | Halogen-free epoxy resin composition and high-flexibility flexible copper clad laminate prepared from same | |
| CN103555242A (en) | Halogen-free flame-retardant epoxy resin composition and high-flexibility halogen-free cover film prepared from same | |
| CN102010567B (en) | Non-halogen and non- phosphate epoxy resin composition and coverage membrane prepared by same | |
| CN101570674B (en) | Halogen-free flame retardant type bonding agent composition | |
| CN101838440B (en) | Non-halogen, non-phosphorous and non-silicone epoxy resin compositions and flexible copper clad laminate prepared thereby | |
| CN102051023A (en) | Halogen-free resin composition and resin-coated copper foil and copper-clad plate prepared from same | |
| CN101851391B (en) | Halogen-free phosphate-free silicon-free epoxy resin composition and cover layer prepared by using same | |
| CN103694639B (en) | A kind of Halogen ageing-resistant epoxy resin composition and prepare the method for mulch film with this resin combination |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |