CN102786704B - Preparation method for black polyimide (PI) film - Google Patents
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Abstract
The invention provides a preparation method for a black polyimide (PI) film. Diamine, dianhydride and black stuffing are taken as raw materials. An addition method is provided with two, one method is that the black stuffing after being processed by coupling agent is added into polyamide acid solution for fully and uniformly mixing up, and the mixture is subjected to a tape casting method to form a film; and the other method is that polyamide acid (PAA) black composite solution is prepared via an in-situ polymerization method, and black PI film is obtained after the solution is subjected to a heat imidization treatment. The prepared PI black film has the advantages of simpleness in operation, excellent process, uniform color and remarkable uniformity of the product. The black PI film can be used as a black covering film, a black static electricity prevention film, a black anti-shielding material and the like, and has wide application in fields of a light-emitting diode (LED), a flexible printed circuit board and the like.
Description
Technical field
The present invention relates to a kind of preparation method of black polyamide thin film, particularly relate to and prepare black covering film by adding black filler.
Background technology
Black PI film is with a long history, applies very extensive.Such as: black belt, black anti-electrostatic adhesive tape, black stiffening plate, black covering film, black speaker voice coil, black label, black pad, black anti-dazzling screen, the anti-shielding material of black, black sound diaphragm, liquid crystal module colligation and a large amount of alternative black PEI films etc.Black covering film is one of series product of black PI film, and compared to common mulch film, it is opaque, and it is good not reflect backlight confidentiality, and color even, homogeneity of product is excellent, can be used for LED illumination, immunity printed circuit board etc.
With regard to the technology of preparing of black covering film, conventional has two kinds of approach: one is be coated in by common glue on black PI film, and two is that special a kind of black glue solution is coated on common PI film.For batch production, the first approach only need change starting material, easy and simple to handle; The second approach then must be started with from formula, and brings certain puzzlement to production operation.
Liu Shengpeng take butanone as solvent, solidifying agent is added by certain equivalence ratio, dissolve transparent after add dispersion agent, (one is high tinting strength colour black to two kinds of carbon blacks, a kind of is high-insulativity carbon black) be placed on mixing machine and grind certain hour, then titanium dioxide is added, phosphonium flame retardant, finally add EP and CTBN, solid content is about 30% ~ 40%(and decides with viscosity), abundant stirring, obtain black epoxy glue, about 15 μm, in 160 DEG C of baking 4min, cool to room temperature, the separate-type paper cut out is attached to be scribbled on the PI film of tackiness agent, obtain black covering film.Gained film is used for the field such as mobile phone, energy-saving illumination, and shortcoming is that carbon black loading is larger, and separate-type paper is more difficult to be attached to glue-line, and this phenomenon all can produce certain impact to punching, boring etc. in FPC processing procedure.
CN101579904A discloses a kind of preparation method of black matt polyimide film.Content comprises: the preparation of polyamic acid solution, the preparation of black paste, the preparation of black matt resin solution and curtain coating, drying and cyclodehydration process.Adding Way has two kinds, and one is added by matt agent in polyamic acid solution fully to stir curtain coating, drying and cyclodehydration and obtain black thin film together with black paste; Another kind method is that matt agent, black paste and diamines first mix, then adds dianhydride and directly prepare black matt polyamic acid solution, and curtain coating, drying and cyclodehydration prepare black thin film.Gained film is applicable to black polyamide thin film major part positioning field, such as, be used as light absorption film, prepare photocuring losser and optical terminus device etc. with it.
CN102219999A discloses a kind of preparation method printing polyimide black film.Step comprises: one, by 2, and 5 adjacent dimethyl, to benzidine and DMF mix and blend, add diphenyl disulfide ether tetracarboxylic dianhydride, the polyamic acid of reaction; Two, add DMF dilution in above-mentioned polyamic acid, add carbon black and activated Calcium carbonate obtains black paste; Three, above-mentioned solution stirring evenly, curtain coating, drying and dehydrating cyclisation obtain 50 μm of polyimide black films.The present invention is under the condition of not sacrificing Kapton thermal characteristics and electric property, add highly active Nano particles of calcium carbonate and carbon black particle, its tack, printing are good, but its film thickness reaches 50 μm, hinder widening of its range of application, be necessary to improve and reduce film thickness.
US20040142191 discloses a kind of black glue solution having halogen type, this black glue solution is applied to common polyimide surface polyimide black film.Black glue solution mixes obtained by brominated epoxy resin, amino terminated butadiene acrylonitrile rubber or nbr carboxyl terminal and carbon black with certain proportion.This film can be used for LED field, and shortcoming is that preparation shows slightly loaded down with trivial details, and film contains haloid element, and the intervention of fire-retardant factor makes its application be restricted.
BPDA, the ODA such as Xue PF synthesize PAA, add the carbon black with acyl chlorides modification, have prepared polyimide black film.Carbon black modified process is as follows: one, carbon black (CB) back flow reaction 4h in HNO3 solution, makes-COOH on its surface grafting, i.e. CB-COOH; Two, react in acyl chlorides, obtain CB-COCl.The modified carbon black of preparation adds in polyamic acid solution, and stir, curtain coating, drying and cyclodehydration obtain laminated film.The method membrane-film preparation process is simple, is convenient to batch production, but has the problem of halogen polyimide black film equally.
Summary of the invention
The object of the invention is to produce Halogen black covering film, improving the deficiency using the method for black glue solution coating to prepare black covering film, thus a kind of preparation method of black polyamide thin film is provided.
Technical scheme of the present invention is: a kind of preparation method of black polyamide thin film, and its concrete steps are as follows:
A, filler modified
The black filler of drying and silane coupling agent, dehydrated alcohol are stirred at 0 ~ 40 DEG C, and ultrasonic, reaction 3 ~ 6h, reacted filler grain, through washing, grinding, drying, obtains modified filler stand-by; The wherein mass ratio 0.02 ~ 0.1:1 of silane coupling agent and black filler; Filler and dehydrated alcohol mass ratio are 0.01 ~ 0.06:1;
The preparation of B, black filler and polyamic acid (PAA) composite solution; Wherein polyamic acid is the polycondensate of diamines and dianhydride, referred to as PAA;
B
1: diamines is added in aprotic polar solvent, stirring makes it dissolve, add modified filler in steps A, gained solution is ultrasonic abundant dispersion 0.5 ~ 4h at 15 DEG C ~ 30 DEG C, 2 ~ 8 batches are divided to add the dianhydride with diamines equimolar amount again, continuously stirring is phase uniformly, and obtained black filler and PAA total mass solid content are the black filler of 12 ~ 25% and the composite solution of PAA;
Or B
2:
I. add diamines in the reactor, make it be dissolved in aprotic polar solvent, temperature controls to stir at 20 ~ 30 DEG C, after it dissolves completely, divide 2 ~ 8 batches and add the dianhydride with diamines equimolar amount, continuously stirring, obtained PAA quality solid content is the PAA solution of 12 ~ 25%;
II. modified filler steps A obtained adds in the PAA solution in step I, and the ultrasonic abundant dispersion 0.5 ~ 4h of temperature control 15 DEG C ~ 30 DEG C, stirs, the composite solution of obtained black filler and PAA;
The preparation of C, black covering film
By step B
1or B
2the composite solution dip-coating of middle preparation is in the non-porous support such as glass plate, steel plate, and put into vacuum drying oven ladder-elevating temperature, cyclodehydration obtains laminated film.
Preferred steps A, B
1be 20KHz ~ 100KHz with the ultrasonic frequency described in II; Step B
1in I, after adding dianhydride, the continuously stirring time is 4 ~ 12h; Step B
1in II, the mass ratio of modified filler and polyamic acid is 0.04 ~ 0.5:1.
The temperature rise rate of the ladder-elevating temperature described in preferred steps C is 2 ~ 5 DEG C/min; First be warmed up to 80 DEG C ~ 120 DEG C constant temperature 30min ~ 90min; Be warmed up to 180 DEG C ~ 220 DEG C constant temperature 30min ~ 90min again; Finally be warmed up to 280 DEG C ~ 380 DEG C constant temperature 30min ~ 90min.
The present invention PAA used is by precursor dianhydride and diamines reactive polymeric and obtaining in described solvent.
Described aprotic polar solvent is preferably N-Methyl pyrrolidone (NMP), DMF (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO) or tetrahydrofuran (THF).
Described diamines is preferably: the flexible aromatic diamines (DAMI) of long-chain, 4, 4 '-diaminodiphenyl oxide (ODA), dimethyl diphenyl methane diamines (DMMDA), 1, two (3-amino-benzene oxygen) benzene (BAPB) of 3-, 4, 4 '-dihydroxyphenyl propane diphenyldiamine (BAPP), perfluor isopropylidene diamine (4-BDAF), 4, 4 '-two (4-amino-benzene oxygen) sulfobenzide (BAPS), 4, 4 '-two (4-amino-benzene oxygen) phenyl ether (BAPE), diamino hexichol (first) ketone (DABP), 4, 4 '-diamino triphenylamine (DATPA), 4, 4 '-diaminodiphenylmethane (MDA), diamino diphenyl sulfone (DDS), 3, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenyl-methane, 3, 3 '-dimethyl-4, 4 '-diaminodiphenyl-methane, 4, , 4 '-diamino-hexichol Oxy-1 ", 4 "-benzene, 4, 4 '-diamino-hexichol Oxy-1 ", 3 "-benzene, 3, 3 '-diamino-hexichol Oxy-1 ", 3 "-benzene or 4, 4 '-diamino-two phenoxy group-4 ", one or both in 4-phenylbenzene isopropyl alkane are blended.
Described dianhydride is preferably pyromellitic acid anhydride (PMDA), and 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride (BPDA), 4,4 '-Biphenyl Ether dianhydride (ODPA), isomery diphenyl sulfide dianhydride (TDPA), triphen diether tetracarboxylic dianhydride (HQDPA), benzophenone tetracarboxylic acid dianhydride (BTDA), benzophenone tetracarboxylic dianhydride (BDPA), hexafluoroisopropylidenyl two metatitanic acid dianhydride (6-FDA) or 3,3 ', 4, one or both in 4 '-sulfobenzide tetracarboxylic anhydride (DSDA) are blended.
Silane coupling agent in the present invention is preferably γ-aminopropyl triethoxysilane (KH550), γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane (KH560), γ-methacryloxypropyl trimethoxy silane (KH570), N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), N-β (aminoethyl)-γ-aminopropyl dimethoxy silane (DL602), the one in vinyltrimethoxy silane (DL171).
It is blended that black filler in the present invention is preferably one or more in carbon black, nigrosine, titanium oxynitrides, titanium suboxide, graphite, carbon fiber powder.
Beneficial effect:
1, the filler that the present invention adopts has good tinting strength, the firm excellent performance of color, can well be dispersed in polyamic acid (PAA) resin, form uniform and stable suspension.
2, the black covering film prepared of the present invention, simple to operate, technique is excellent, and volume specific resistance is 10
12Ω cm, has good insulating property, and the finished product rate made is high, and mechanical property is excellent.
3, the film produced of the present invention, thermal characteristics is stablized, and its thermal expansivity (CTE) can reach 1.71 × 10
-6k
-1, through thermogravimetric analysis, heat decomposition temperature is all more than 500 DEG C, and use range is extensive.
Accompanying drawing explanation
The mechanical property figure of the film of the filler different mass percentage composition of Fig. 1 obtained by example 5-9;
The thermal expansivity figure of the film of the filler different mass percentage composition of Fig. 2 obtained by example 5-9;
The transmittance figure of the film of the filler different mass percentage composition of Fig. 3 obtained by example 5-9.
Embodiment
To contribute to understanding the present invention by following example, but not limit content of the present invention.
Embodiment 1
Fully dry 5.9287g carbon black and silane coupling agent (KH550) 0.3016g, 100g dehydrated alcohol are stirred at 20 DEG C, and ultrasonic reaction 3h, ultrasonic frequency is 40KHz, and reacted filler grain is through washing, grinding, drying, stand-by.
Take 11.9657g4,4 '-diaminodiphenyl oxide (ODA), be dissolved in 75.0027gN, in N '-dimethyl ethanamide (DMAc), stir at 20 DEG C, then 3 batches are divided to add and the pyromellitic dianhydride of ODA equimolar amount (PMDA) 13.0342g altogether, continue to stir, along with the continuous dissolving of dianhydride monomer, the viscosity of polymkeric substance also constantly increases, monomer all dissolves rear continuation and stirs 3h at normal temperatures, and obtained solid content (massfraction) is the PAA solution of 25%.The carbon black 5.0097g taking above-mentioned process adds in PAA solution, and 15 DEG C are stirred ultrasonic 0.5h, and ultrasonic frequency is 80KHz.
By composite solution dip-coating on glass plate, put into vacuum drying oven ladder-elevating temperature, temperature rise rate is 2 DEG C/min(90 DEG C × 45min, 200 DEG C × 60min, 300 DEG C × 70min), obtain the PI/ carbon black film of cyclodehydration.
Embodiment 2
Fully dry 5.9880g carbon black and silane coupling agent (KH570) 0.436g, 120g dehydrated alcohol are stirred at 10 DEG C, and ultrasonic reaction 5h, ultrasonic frequency is 20KHz, and reacted filler grain is through washing, grinding, drying, stand-by.
The carbon black taking 5.2004g puts into 79.9986gN, in N '-dimethyl ethanamide (DMAc) solvent, at 18 DEG C, ultrasonic agitation 3h ultrasonic frequency 25KHz, adds 5.6723g4,4 '-diaminodiphenyl oxide (ODA), after it dissolves completely, divide 5 batches and add the dianhydride monomer 3,3 ' with ODA equimolar amount, 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is 9.1277g altogether, continues to stir 2h, and obtained solid content (filler and PAA total mass) is the PAA/ carbon black composite solution of 20%.
By the dip-coating of PAA/ carbon black composite solution on glass plate, put into vacuum drying oven ladder-elevating temperature, temperature rise rate is 4 DEG C/min(100 DEG C × 60min, 210 DEG C × 75min, 320 DEG C × 60min), obtain the PI/ carbon black film of cyclodehydration.
Embodiment 3
Fully dry 5.606g graphite and silane coupling agent (KH560) 0.1128g, 140g dehydrated alcohol are stirred at 0 DEG C, and ultrasonic reaction 4h, ultrasonic frequency is 60KHz, and reacted filler grain is through washing, grinding, drying, stand-by.
The graphite taking 3.9605g puts into 88.0012gN, in N '-dimethyl ethanamide (DMAc) solvent, ultrasonic agitation 0.5h ultrasonic frequency 100KHz at 28 DEG C, add 4.7208g octylated diphenylamine (ODPA), after it dissolves completely, divide 7 batches to add and the dianhydride monomer pyromellitic dianhydride (PMDA) of ODPA equimolar amount 3.3192g altogether, continue to stir 12h, obtained solid content (filler and PAA total mass) is the PAA/ carbon black composite solution of 12%.
By the dip-coating of PAA/ filler composite solution on stainless steel curtain coating plate, put into vacuum drying oven ladder-elevating temperature, temperature rise rate is 3 DEG C/min(120 DEG C × 30min, 180 DEG C × 90min, 280 DEG C × 90min), obtain the PI/ graphite laminated film of cyclodehydration.
Embodiment 4
Fully dry 2.036g titanium oxynitrides and silane coupling agent (KH550) 0.0608g, 100g dehydrated alcohol are stirred at 40 DEG C, and ultrasonic reaction 6h, ultrasonic frequency is 100KHz, and reacted filler grain is through washing, grinding, drying, stand-by.
Take 7.1795g4,4 '-diaminodiphenyl oxide (ODA), be dissolved in 85.0027g N, in N '-dimethyl ethanamide (DMAc), stir at 30 DEG C, then 2 batches are divided to add and the pyromellitic dianhydride of ODA equimolar amount (PMDA) 7.8205g altogether, continue to stir, along with the continuous dissolving of dianhydride monomer, the viscosity of polymkeric substance also constantly increases, monomer all dissolves rear continuation and stirs 10h at normal temperatures, and obtained solid content (massfraction) is the PAA solution of 15%.The titanium oxynitrides 1.5010g taking above-mentioned process adds in PAA solution, 28 DEG C of stirrings, and ultrasonic 4h, ultrasonic frequency is 24KHz.
By composite solution dip-coating on glass plate, put into vacuum drying oven ladder-elevating temperature, temperature rise rate is 3 DEG C/min(110 DEG C × 50min, 190 DEG C × 80min, 380 DEG C × 30min), obtain the PI/ titanium oxynitrides film of cyclodehydration.
Embodiment 5
Fully dry 2.6032g nigrosine and vinyltrimethoxy silane (DL171) 0.2590,200g dehydrated alcohol are stirred at 30 DEG C, and ultrasonic reaction 6h, ultrasonic frequency is 80KHz, and reacted filler grain is through washing, grinding, drying, stand-by.
The nigrosine taking 0.6503g puts into 87.1200gN, in N '-dimethyl ethanamide (DMAc) solvent, ultrasonic agitation 4h at 25 DEG C, ultrasonic frequency 50KHz, adds 5.9111g4,4 '-diaminodiphenyl oxide (ODA), after it dissolves completely, divide 6 batches to add and the dianhydride monomer pyromellitic dianhydride (PMDA) of ODPA equimolar amount 6.4389g altogether, continue to stir 8h, obtained solid content (filler and PAA total mass) is the PAA/ carbon black composite solution of 13%.
By the dip-coating of PAA/ filler composite solution on stainless steel curtain coating plate, put into vacuum drying oven ladder-elevating temperature, temperature rise rate is 5 DEG C/min(80 DEG C × 90min, 220 DEG C × 30min, 360 DEG C × 60min), obtain the PI/ nigrosine laminated film of cyclodehydration.
Embodiment 6-9
Embodiment 6-9 is under the experiment condition identical with embodiment 5, and the content changing filler carbon black is 10%, 12%, 18%, 30%.
The mechanical property of the film of the filler different mass percentage composition obtained by example 5-9 as shown in Figure 1; Fig. 1 shows, along with the increase of the mass percentage of filler, the Young's modulus of film significantly rises, and tensile strength has the decline of some amount.
The thermal expansivity of the film of the filler different mass percentage composition obtained by example 5-9 as shown in Figure 2; Fig. 2 shows, along with the increase of the mass percentage of filler, the thermal expansivity of film presents downward trend.
The transmittance of the film of the filler different mass percentage composition obtained by example 5-9 as shown in Figure 3; In Fig. 3, along with the increase of the mass percentage of filler, the transmittance of film declines gradually, shows that the covering occlusion effect of film strengthens.
Carry out transmittance test to the corona-resistant polyimide film obtained by embodiment 1-9 respectively, result is as shown in table 1.
The transmittance of table 1 black polyamide thin film
Claims (8)
1. a preparation method for black polyamide thin film, its concrete steps are as follows:
A, filler modified
Black filler and silane coupling agent, dehydrated alcohol are stirred at 0 ~ 40 DEG C, and ultrasonic, reaction 3 ~ 6h, reacted filler grain, through washing, grinding, drying, obtains modified filler stand-by; The wherein mass ratio 0.02 ~ 0.1:1 of silane coupling agent and black filler; Filler and dehydrated alcohol mass ratio are 0.01 ~ 0.06:1;
The preparation of B, black filler and polyamic acid composite solution; Wherein polyamic acid is the polycondensate of diamines and dianhydride, referred to as PAA;
B1: diamines is added in aprotic polar solvent, stir and make it dissolve, add the modified filler obtained in steps A, wherein the mass ratio of modified filler and polyamic acid is 0.04 ~ 0.5:1; Gained solution is ultrasonic abundant dispersion 0.5 ~ 4h at 15 DEG C ~ 30 DEG C, then divides 2 ~ 8 batches to add the dianhydride with diamines equimolar amount, and continuously stirring is phase uniformly, and obtained black filler and PAA total mass solid content are the composite solution of 12 ~ 25% black fillers and PAA;
Or
B2：
I. add diamines in the reactor, make it be dissolved in aprotic polar solvent, temperature controls to stir at 20 ~ 30 DEG C, after it dissolves completely, divide 2 ~ 8 batches and add the dianhydride with diamines equimolar amount, continuously stirring, obtained PAA quality solid content is the PAA solution of 12 ~ 25%;
II. added by the modified filler that steps A obtains in the PAA solution in step I, wherein the mass ratio of modified filler and polyamic acid is 0.04 ~ 0.5:1; The ultrasonic abundant dispersion 0.5 ~ 4h of temperature control 15 DEG C ~ 30 DEG C, stirs, the composite solution of obtained black filler and PAA;
The preparation of C, black polyamide thin film
The black filler prepared by step B1 or B2 and the composite solution dip-coating of PAA are in non-porous support, and put into vacuum drying oven ladder-elevating temperature, cyclodehydration obtains black polyamide thin film; The temperature rise rate of wherein said ladder-elevating temperature is 2 ~ 5 DEG C/min; First be warmed up to 80 DEG C ~ 120 DEG C constant temperature 30min ~ 90min; Be warmed up to 180 DEG C ~ 220 DEG C constant temperature 30min ~ 90min again; Finally be warmed up to 280 DEG C ~ 380 DEG C constant temperature 30min ~ 90min.
2. preparation method according to claim 1, is characterized in that the ultrasonic frequency described in steps A, B1 and II is 20kHz ~ 100kHz; In step B1 and I, after adding dianhydride, the continuously stirring time is 4 ~ 12h.
3. preparation method according to claim 1, is characterized in that described aprotic polar solvent is N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
4. preparation method according to claim 1, it is characterized in that described diamines is: 4, 4 '-diaminodiphenyl oxide, dimethyl diphenyl methane diamines, 1, two (3-amino-benzene oxygen) benzene of 3-, 4, 4 ' dihydroxyphenyl propane diphenyldiamine, perfluor isopropylidene diamine, 4, 4 '-two (4-amino-benzene oxygen) sulfobenzide, 4, 4 ' two (4-amino-benzene oxygen) phenyl ether, diaminobenzophenone, 4, 4 '-diamino triphenylamine, 4, 4 ' diaminodiphenylmethane, diamino diphenyl sulfone, 3, 4 '-diaminodiphenyl oxide, 4, 4 '-diaminodiphenyl-methane, 3, 3 '-dimethyl-4, 4 '-diaminodiphenyl-methane, 4, 4 '-diamino-hexichol Oxy-1 ", 4 "-benzene, 4, 4 '-diamino-hexichol Oxy-1 ", 3 "-benzene, 3, 3 '-diamino-hexichol Oxy-1 ", 3 "-benzene or 4, 4 '-diamino-two phenoxy group-4 ", one or both in 4-phenylbenzene isopropyl alkane are blended.
5. preparation method according to claim 1, it is characterized in that described dianhydride is: pyromellitic acid anhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 4,4 '-Biphenyl Ether dianhydride, isomery diphenyl sulfide dianhydride, triphen diether tetracarboxylic dianhydride, benzophenone tetracarboxylic acid dianhydride, benzophenone tetracarboxylic dianhydride, hexafluoroisopropylidenyl two metatitanic acid dianhydride or 3,3 ', 4, one or both in 4 '-sulfobenzide tetracarboxylic anhydride are blended.
6. preparation method according to claim 1, it is characterized in that described silane coupling agent is the one in γ-aminopropyl triethoxysilane, γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropyl dimethoxy silane or vinyltrimethoxy silane.
7. preparation method according to claim 1, is characterized in that described black filler is that one or more in carbon black, nigrosine, titanium oxynitrides, titanium suboxide, graphite or carbon fiber powder are blended.
8. preparation method according to claim 1, is characterized in that non-porous support is glass plate or steel plate.
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100526369C (en) * | 2007-05-31 | 2009-08-12 | 上海市合成树脂研究所 | Production of black polyamide thin film |
| CN101579904B (en) * | 2009-06-15 | 2011-06-08 | 上海市合成树脂研究所 | Preparation method of black matt polyimide film |
| CN102219999A (en) * | 2010-04-16 | 2011-10-19 | 苏州安洁科技股份有限公司 | Preparation method of printable black polyimide film |
-
2012
- 2012-08-06 CN CN201210277962.2A patent/CN102786704B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112480404A (en) * | 2020-11-27 | 2021-03-12 | 株洲时代新材料科技股份有限公司 | Magnetic heat-conducting polyimide composite material and preparation method thereof |
| CN112480404B (en) * | 2020-11-27 | 2022-12-13 | 株洲时代新材料科技股份有限公司 | Magnetic heat-conducting polyimide composite material and preparation method thereof |
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| CN102786704A (en) | 2012-11-21 |
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