CN1786052A - Preparation method of polyimide - Google Patents
Preparation method of polyimide Download PDFInfo
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- CN1786052A CN1786052A CN 200410097120 CN200410097120A CN1786052A CN 1786052 A CN1786052 A CN 1786052A CN 200410097120 CN200410097120 CN 200410097120 CN 200410097120 A CN200410097120 A CN 200410097120A CN 1786052 A CN1786052 A CN 1786052A
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- polyamic acid
- polyimide
- cyclization
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- copper foil
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Abstract
The present invention relates to a production method of polyimide. Said method includes the following steps: making diacid anhydride react with diamine to form polyamic acid, coating the polyamic acid on the supporting body by means of coating or casting mode, removing solvent and controlling volatile component content of polyamic acid to below 10wt%, controlling tensile force to below 20kgf/sq.cm, making rolling up, feeding the above-mentioned material into high-temperature drying oven, utilizing gradient temperature to heat so as to make polyamic acid undergo the processes of dehydration and cyclization to form polyimide.
Description
Technical field
The present invention is relevant to coat the novel method of making polyimide on the support by coating or mold methods such as (casting), especially obtains the novel method for making that outward appearance adds the polyimide of soft laminated plates about utilizing the gradient temperature heating after reeling by the volatile component content of control polyamic acid and with specific tensile with high yield.
Background technology
Polyimide is the extremely wide high temperature material of purposes, and it is insoluble to solvent itself and does not also melt, and can make film from the polyamic acid of solution form.Or can be used as the insulating material of sticking agent or electric wire, or can form the finished product kenel earlier after imidization.Polyimide has high heat-resistant quality, can bear all encapsulation conditions, can tolerate the test of metallized temperature, and its have electrical specification, surface and overall leakage rate low, also be applicable to HF link.
Owing to these characteristics of polyimide are widely used in fields such as communication, consumption electronic products, personal communication assistant, gas separation membrane.Polyimide by on the tinsel of coating Copper Foil for example etc., is made flexible circuit board, and is applied on the electronics of mobile computer, consumption electronic products, mobil phone etc. usually.
When making flexible circuit board, adopt at present following method: (1) is coated on polyamic acid resin on the tinsel or on the Kapton, make the polyamic acid cyclisation form polyimide by generally being higher than 350 ℃ high-temperature infrared ray or adding hotblast stove continuously, but under this high temperature because the thermal expansion coefficient difference of tinsel and polyimide, regular meeting causes the polyimide film warpage of gained, the not good yield that makes of rolling reduces when causing reeling this polyimide film, and the equipment used costliness; (2) be coated on polyamic acid resin on the tinsel or on the Kapton, to weave the iron gauze pad in these tinsel both sides, enter generally to be higher than 350 ℃ high-temperature infrared ray or to add hotblast stove with batch formula and make the polyamic acid cyclisation form polyimide, but under this high temperature, should braiding iron net regular meeting be out of shape, cause the polyimide finished product to produce fold, reduce yield; And (3) are coated on polyamic acid resin on the tinsel or on the Kapton, separate with resistant to elevated temperatures release film or Kapton, entering high-temperature infrared ray or adding hotblast stove makes the polyamic acid cyclisation form polyimide, but the service temperature of this method can not be too high otherwise will makes the release film fusion or polyimide resin is stained with glutinous, make the finished product outward appearance not good, then can reduce the cyclisation rate but service temperature is low, if desire to reach the cyclisation rate more than 95%, then must the longer operating time, and can reduce production efficiency.
In view of above-mentioned, the inventor etc. are in order to improve the shortcoming of above-mentioned prior art method, and the process conditions that polyamic acid is cyclized into polyimide is carried out broad research, thereby finishes the present invention.
Summary of the invention
The novel method for making of the relevant a kind of polyimide of the present invention, comprise make dicarboxylic anhydride and diamine reactant form polyamic acid (polyamic acid) after, by polyamic acid coating or mold methods such as (casting) are coated on the support, remove again solvent by control polyamic acid volatile content below 10 weight %, and with tension control at 20kgf/cm
2After below reeling, enter high temperature oven, utilize the gradient temperature heating and make the polyamic acid cyclodehydration become polyimide, can obtain productive rate height, the good soft laminated plates of outward appearance to criticize the formula mode.
The method for making of polyamic acid is dicarboxylic anhydride and diamine reactant to be formed contain-NH-CO-functional group and carboxylic acid group's polymkeric substance among the present invention.And alleged cyclization among the present invention, be further make this-NH-CO-functional group and this carboxylic acid group carry out dehydrating condensation and form the process of cyclic group, is also referred to as inferior amidate action.
According to method of the present invention, can high yield and high cyclisation rate obtain the polyimide resin tinsel mantle that outward appearance is good and mechanical properties is excellent of no wrinkle.
Embodiment
The dicarboxylic anhydride example of preparation polyamic acid can be given an example as the two acid anhydrides of (but being not limited to) aromatics pyromellitic dianhydride (PMDA) for example among the present invention; 4,4-two phthalandione dianhydrides (BPDA); 4,4-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA); 1-(trifluoromethyl)-2; 3,5,6-benzene tertacarbonic acid dianhydride (P3FDA); 1; two (trifluoromethyl)-2,3 of 4-, 5; 6-benzene tertacarbonic acid dianhydride (P6GDA); 1-(3 '; 4 '-dicarboxyl phenyl)-1,3,3-trimethylammonium indane-5; the 6-dicarboxylic acid dianhydride; 1-(3 '; 4 '-dicarboxyl phenyl)-1,3,3-trimethylammonium indane-6; the 7-dicarboxylic acid dianhydride; 1-(3 '; 4 '-dicarboxyl phenyl)-and 3-methyl indan-5, the 6-dicarboxylic acid dianhydride; 1-(3 ', 4 '-dicarboxyl phenyl)-3-methyl indan-6; the 7-dicarboxylic acid dianhydride; 2; 3,9,10-perylene tetracarboxylic dianhydride; 1; 4; 5,8-naphthalene tetracarboxylic acid dianhydride; 2,6-dichloronaphtalene-1; 4; 5, the 8-tetracarboxylic dianhydride; 2,7-dichloronaphtalene-1; 4; 5, the 8-tetracarboxylic dianhydride; 2,3; 6; 7-Tetrachloronaphthalene-2,4,5; the 8-tetracarboxylic dianhydride; luxuriant and rich with fragrance-1; 8,9, the 10-tetracarboxylic dianhydride; 3; 3 '; 4,4 '-benzophenone tetracarboxylic dianhydride; 1,2 '; 3; 3 '-benzophenone tetracarboxylic dianhydride; 3,3 ', 4; 4 '-biphenyl tetracarboxylic dianhydride; 3; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride; 2; 2 '; 3,3 '-biphenyl tetracarboxylic dianhydride; 4,4 '-isopropylidene, two phthalandione dianhydrides; 3; 3 '-isopropylidene, two phthalandione dianhydrides; 4; 4 '-oxygen base, two phthalandione dianhydrides; 4,4 '-alkylsulfonyl, two phthalandione dianhydrides; 3,3 '-oxygen base, two phthalandione dianhydrides; 4; 4 '-methylene radical, two phthalandione dianhydrides; 4; 4 '-sulfenyl, two phthalandione dianhydrides; 4,4 '-ethylene phthalandione dianhydride; 2,3; 6; 7-naphthalene tetracarboxylic acid dianhydride; 1,2,4; 5-naphthalene tetracarboxylic acid dianhydride; 1; 2,5,6-naphthalene tetracarboxylic acid dianhydride; benzene-1; 2; 3, the 4-tetracarboxylic dianhydride; pyrazine-2,3; 5; 6-tetracarboxylic dianhydrides etc. wherein are preferably pyromellitic dianhydride (PMDA); 4,4-two phthalandione dianhydrides (BPDA); 4; 4-hexafluoroisopropyli,ene two phthalandione dianhydrides (6FDA); 1-(trifluoromethyl)-2; 3,5,6-benzene tertacarbonic acid dianhydride (P3FDA); 1; two (trifluoromethyl)-2 of 4-; 3,5,6-benzene tertacarbonic acid dianhydride (P6GDA).
The diamines example of preparation polyamic acid can be given an example as (but being not limited to) aromatics diamine for example 4 among the present invention; 4 '-oxygen base pentanoic (ODA); 5-amido-1-(4 '-aminocarbonyl phenyl)-1; 3; 3-trimethylammonium indane; 6-amido-1-(4 '-aminocarbonyl phenyl)-1; 3; 3-trimethylammonium indane; 4; 4 '-methylene-bis (neighbour-chloroaniline); 3; 3 '-dichloro diphenylamine; 3; 3 '-alkylsulfonyl pentanoic; 4; 4 '-two amido benzophenone; 1; 5-two amido naphthalenes; two (4-aminocarbonyl phenyl) diethylsilane; two (4-aminocarbonyl phenyl) diphenyl silane; two (4-aminocarbonyl phenyl) ethyl phosphine oxide; N-(two (4-aminocarbonyl phenyl))-N-methylamine; N-(two (4-aminocarbonyl phenyl))-N-phenyl amine; 4; 4 '-methylene-bis (2-aminotoluene); 4; 4 '-methylene-bis(2methoxyaniline); 5; 5 '-methylene-bis (2-amino-phenol); 4; 4 '-methylene-bis (2-aminotoluene); 4; 4 '-oxygen base two (2-anisidine); 4; 4 '-oxygen base two (2-chloroaniline); 2; 2 '-two (4-amino-phenols); 5; 5 '-oxygen base two (2-amino-phenol); 4; 4 '-sulfenyl two (2-aminotoluene); 4; 4 '-sulfenyl two (2-anisidine); 4; 4 '-sulfenyl two (2-chloroaniline); 4; 4 '-alkylsulfonyl two (2-aminotoluene); 4; 4 '-alkylsulfonyl two (2-phenetidine); 4; 4 '-alkylsulfonyl two (2-chloroaniline); 5; 5 '-alkylsulfonyl two (2-amino-phenol); 3; 3 '-dimethyl-4; 4 '-two amido benzophenone; 3; 3 '-dimethoxy-4 '; 4 '-two amido benzophenone; 3; 3 '-two chloro-4; 4 '-two amido benzophenone; 4; 4 '-benzidine; between-phenylenediamine; p-phenylenediamine; 4; 4 '-methylene dianiline (MDA); 4; 4 '-sulfenyl pentanoic; 4; 4 '-alkylsulfonyl pentanoic; 4; 4 '-isopropylidene pentanoic; 3; 3 '-tolidine; 3; 3 '-dimethoxy benzidine; 3; 3 '-dicarboxylate biphenyl amine; 2; 4-tolyl diamines; 2; 5-tolyl diamines; 2; 6-tolyl diamines; between-the xylyl diamines; 2; 4-two amidos-5-toluene(mono)chloride; 2,4-two amidos-6-toluene(mono)chloride etc.Be preferably 4,4 '-oxygen base pentanoic (ODA).
The reaction of this dicarboxylic anhydride and diamines can be carried out in aprotic polar solvent, and there is no particular restriction for the kind of aprotic polar solvent, only otherwise get final product with reactant and product reaction.Specific examples can be given an example as N,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF), tetrahydrofuran (THF) (THF), dioxan, chloroform (CHCl
3), methylene dichloride etc.Wherein better use 1-methyl-2-pyrrolidone (NMP) and N,N-dimethylacetamide (DMAc).
The reaction of this dicarboxylic anhydride and diamines is generally carried out in the temperature range of room temperature to 70 ℃, and the ratio of this aromatics diamine and the two acid anhydrides of aromatics is between 0.5 to 2.0 scope, 0.75～1.25 scope more fortunately.
According to method of the present invention, behind dicarboxylic anhydride and diamine reactant formation polyamic acid, methods such as polyamic acid resin coating or mold are coated on the supporter, remove again solvent contained in it by the volatile content in the control polyamic acid below 10 weight %.Utilize subsequently and cover the upholder that the volume machine will be coated with polyamic acid and face mode interior or outwardly, cover and roll up on the steel pipe that covers the volume machine with coated with resins, with tension control in 20kgf/cm
2Below, loose winding leaves at interval each interlayer subsequently, makes thermal convection enter each interlayer and reaches the purpose of cyclisation.Cover volume length and can be preferably 20 to 120 meters length up to 150 meters.
Used upholder can use for example tinsels such as Kapton such as Kapton, Upliex, Copper Foil, aluminium foil, stainless steel foil, nickel foil in the inventive method, uses Copper Foil more usually.
Coiling thing with loose winding moves in the baking oven subsequently, makes the oven temperature gradient be controlled at 100 to 380 ℃ scope, that is from 100 ℃ initial, be warming up to up to 380 ℃ gradually with 1-2 ℃/minute heat-up rate after, cooled.From between 160 to 380 ℃ temperature raising period, can stop tens of minutes at several specified temps respectively, for example earlier initial and stop after for example about 30 minutes with 160 to 180 ℃, with 2 ℃/minute heat-up rates be warming up to gradually about 210 to 230 ℃ stop for example about 30 minutes again after, being warming up to about 270 to 290 ℃ gradually with 2 ℃/minute heat-up rate again stopped for example about 30 minutes again, not only be warming up to about 340 to 350 ℃ but also stopped for example about 30 minutes gradually subsequently with 2 ℃/minute heat-up rate, be warming up to up to 370 ℃ at last and after stopping about 10 minutes, cooled off.
In the cyclization process of the present invention, also can add catalyst for example triethylamine and diacetyl oxide etc., to quicken cyclization.When using catalyst in cyclization process, used gradient temperature can be relatively low.
When upholder uses Copper Foil,, heat in the process of cyclisation more fortunately in the baking oven for avoiding the Copper Foil oxidation, be blown into for example nitrogen of rare gas element, the oxygen concentration in the baking oven remained on below the 1.0 volume %, below the better 0.5 volume %, better be lower than 0.1 volume %, can prevent the Copper Foil oxidation stain.
In the inventive method, pass through in order to thermal convection, also can after coiling is finished, be removed again every several meters insertion one level and smooth bars during reeling for each interlayer that makes the coiling thing leaves at interval.
Below will further specify the present invention with embodiment and comparative example, in these embodiment and the comparative example, the measuring method of the measuring method of fugitive constituent and cyclisation rate (imidization rate) is as follows:
The measuring method of fugitive constituent
The resin metallic foil sample of getting 10 centimeters * 10 centimeters accurately is weighed as W1, with this sample insert last 20 minutes in 220 ℃ of baking ovens after, take out and accurately to be weighed as W2, and be W3 to the tinsel samples weighing of same 10 centimeters * 10 centimeters uncoated resin in addition.Calculate fugitive constituent % with following formula.
Fugitive constituent (%)=(W1-W2)/(W1-W3) * 100%
The measuring method of cyclisation rate (imidization rate):
Measure the 1720cm of resin with FTIR (Fourier's infrared spectrometer) in temperature T
-1With 1500cm
-1Absorption area ratio ([area
(1720cm-1)/ area
(1500cm-1)] T), measure the 1720cm of resin after 350 ℃ of temperature are lasted 1 hour with FTIR subsequently
-1With 1500cm
-1Absorption area ratio ([area
(1720cm-1)/ area
(1500cm-1)] T
1), with following formula ring rate (%):
Cyclisation rate (%)=[area
(1720cm-1)/ area
(1500cm-1)] the T/[area
(1720cm-1)/ area
(1500cm-1)] T
1* 100%
Embodiment 1
Make pyromellitic dianhydride (PMDA) and 4,4 '-oxygen base pentanoic (ODA) use N-Methyl pyrrolidone (NMP) is 15% polyamic acid resin as the solid composition of acquisition behind the solvent reaction, utilize coating machine to coat on 18 micron thickness, the wide 520 millimeters Copper Foil, utilizing hot blast or IR baking oven that nmp solvent is steamed removes, the solvent of surveying the upholder resin is 3.2 weight %, utilization is covered the Copper Foil that the volume machine will be coated with polyamic acid resin and is wound on the steel pipe, and tension control is at 20kgf/cm
2Below, every coiling inserts a level and smooth bar for 15 meters reeling simultaneously, reels altogether after 100 meters, after outmost turns is fixed with Kapton Tape, removes this level and smooth bar and makes this Copper Foil loose winding.Move into feeding nitrogen and control oxygen content subsequently in the baking oven below 0.1%, heat cyclization with following thermograde.
Cyclisation conditions:
1.180 ℃ 30 minutes (being warming up to 220 ℃) of stop with 30 minutes
2.220 ℃ 30 minutes (being warming up to 280 ℃) of stop with 30 minutes
3.280 ℃ 30 minutes (being warming up to 350 ℃) of stop with 30 minutes
4.350 ℃ 30 minutes (being warming up to 370 ℃) of stop with 10 minutes
5.370 ℃ 10 minutes (cooling) of stop
Utilize the method for above-mentioned measurement cyclisation rate to carry out the measurement of cyclisation rate and check outward appearance subsequently.The result is as shown in table 1.
Embodiment 2
Make pyromellitic dianhydride (PMDA) and 4,4 '-oxygen base pentanoic (ODA) use N-Methyl pyrrolidone (NMP) is 15% polyamic acid resin as the solid composition of acquisition behind the solvent reaction, in this resin, add triethylamine and diacetyl oxide as catalyst, utilize coating machine to coat on 18 micron thickness, the wide 520 millimeters Copper Foil, utilizing hot blast or IR baking oven that nmp solvent is steamed removes, the solvent of surveying the upholder resin is 5.3 weight %, utilization is covered the Copper Foil that the volume machine will be coated with polyamic acid resin and is wound on the steel pipe, and tension control is at 20kgf/cm
2Below, every coiling inserts a level and smooth bar for 15 meters reeling simultaneously, reels altogether after 100 meters, after outmost turns is fixed with Kapton Tape, removes this level and smooth bar and makes this Copper Foil loose winding.Move into feeding nitrogen and control oxygen content subsequently in the baking oven below 0.1%, heat cyclization with following thermograde.
Cyclisation conditions:
1.120 ℃ 30 minutes (being warming up to 180 ℃) of stop with 30 minutes
2.180 ℃ 30 minutes (being warming up to 250 ℃) of stop with 30 minutes
3.250 ℃ 30 minutes (being warming up to 300 ℃) of stop with 30 minutes
4.300 ℃ 10 minutes (cooling) of stop
Utilize the method for above-mentioned measurement cyclisation rate to carry out the measurement of cyclisation rate and check outward appearance subsequently.The result is as shown in table 1.
Embodiment 3 and 4
Carry out as embodiment 1 described condition, but the volatile content of resin is controlled to be 3.3 weight % and 3.5 weight % respectively in embodiment 3 and embodiment 4.Gained the results are shown in table 1.
Comparative example 1
Carry out as embodiment 1 described condition, but the iron net that the volatile content of resin is controlled at 3.4 weight % and utilizes 40 meshes is as spacer, gained the results are shown in following table 1.
Comparative example 2
Carry out as embodiment 1 described condition, but the volatile content of resin is controlled at 3.7 weight % and utilizes the Upilex polyimide film as spacer, gained the results are shown in following table 1.
Comparative example 3
Carry out as embodiment 1 described condition, but the volatile content of resin is controlled at 3.5 weight % and utilizes the Kapton polyimide film as spacer, gained the results are shown in following table 1.
Comparative example 4
Carry out as embodiment 1 described condition, but the volatile content of resin is controlled at 11 weight %, gained the results are shown in following table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Copper Foil length (m) | 100 | 100 | 50 | 120 | 50 | 50 | 50 | 50 |
| Copper Foil width (mm) | 250 | 250 | 520 | 250 | 250 | 250 | 250 | 250 |
| Partition | Do not have | Do not have | Do not have | Do not have | The iron net of 40 meshes | The Upilex polyimide film | The Kapton polyimide film | Do not have |
| Fugitive constituent (weight %) | 3.2 | 5.3 | 3.3 | 3.5 | 3.4 | 3.7 | 3.5 | 11 |
| Outer ring cyclisation rate (%) | ＞100％ | ＞100％ | 98％ | ＞100％ | ＞100％ | ＞100％ | ＞100％ | ＞100％ |
| Inner ring cyclisation rate (%) | 98％ | 96％ | 96％ | 96％ | 98％ | 98％ | 98％ | 98％ |
| Outward appearance | The good no wrinkle of outward appearance | The good no wrinkle of outward appearance | The good no wrinkle of outward appearance | The good no wrinkle of outward appearance | Iron net distortion therefore appearance poor has wrinkle | Polyimide film dilatancy appearance poor has horizontal wrinkle | Polyimide film dilatancy appearance poor has horizontal wrinkle | Copper foil surface has is stained with glutinous resin, and outward appearance is not good |
By the data presentation of table 1, the inventive method of embodiment 1 to 4, is not situated between simultaneously and carries out cyclization by spacer below 10 weight % by the volatile content of control resin, and it is good and do not have a Kapton of wrinkle to obtain outward appearance.On the contrary, comparative example 1 to 3, though the solvent of resin also is controlled at below the 10 weight %, but because it utilizes the spacer as iron net or polyimide in the heating cyclization process, because the thermal expansion coefficient difference of these spacers in heat-processed and between Copper Foil, cause the formed polyimide resin film of cyclisation to produce the outward appearance wrinkle and not good.In the comparative example 4, though be not situated between by spacer, because the solvent of resin is higher than 10 weight %, therefore cause in the cyclization process again, Copper Foil has resin to be stained with glutinous phenomenon so outward appearance is also not good.
By above-mentioned data as can be known, the novel cyclization method of polyimide of the present invention, can high yield and high cyclisation rate obtain the polyimide resin tinsel mantle that outward appearance is good and mechanical properties is excellent of no wrinkle.
Claims (9)
1. the method for making of a polyimide, comprise make dicarboxylic anhydride and diamine reactant form polyamic acid after, by polyamic acid coating or mat molding method are coated on the support, remove again solvent by the volatile content of control polyamic acid below 10 weight %, and with tension control at 20kgf/cm
2After below reeling, enter high temperature oven, make the polyamic acid cyclodehydration become polyimide from 100 to 380 ℃ scope gradient-heated in the gradient increased temperature mode in batch formula mode.
2. method as claimed in claim 1, wherein dicarboxylic anhydride and diamine reactant are to carry out under catalyst exists according to circumstances.
3. method as claimed in claim 2, wherein this catalyst is to be selected from least a of triethylamine and diacetyl oxide or its mixture.
4. method as claimed in claim 1, wherein the volatile content of this polyamic acid is to be controlled at below 8% weight.
5. method as claimed in claim 1, wherein this support carrier is at least a tinsel that is selected from Kapton, Copper Foil, aluminium foil, stainless steel foil, nickel foil.
6. method as claimed in claim 5, wherein this support carrier is a Copper Foil.
7. method as claimed in claim 6, wherein this cyclization is to carry out in oxygen content is lower than the rare gas element of 1.0 volume %.
8. method as claimed in claim 6, wherein this cyclization is to carry out in oxygen content is lower than the rare gas element of 0.5 volume %.
9. method as claimed in claim 6, wherein this cyclization is to carry out in oxygen content is lower than the rare gas element of 0.1 volume %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100971204A CN1305933C (en) | 2004-12-07 | 2004-12-07 | Preparation method of polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100971204A CN1305933C (en) | 2004-12-07 | 2004-12-07 | Preparation method of polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1786052A true CN1786052A (en) | 2006-06-14 |
| CN1305933C CN1305933C (en) | 2007-03-21 |
Family
ID=36783669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100971204A Active CN1305933C (en) | 2004-12-07 | 2004-12-07 | Preparation method of polyimide |
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|---|---|
| CN (1) | CN1305933C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145985A (en) * | 2012-12-09 | 2013-06-12 | 上海飞凯光电材料股份有限公司 | Preparation of polyimide resin and application in high-temperature-resistant optical fiber coatings thereof |
| CN103219067A (en) * | 2012-12-22 | 2013-07-24 | 西安交通大学 | Anisotropic conducting film based on carbon nano tube array and preparation method thereof |
| CN105665250A (en) * | 2016-01-28 | 2016-06-15 | 深圳市弘海电子材料技术有限公司 | Production line for preparing flexible non-adhesive polyimide copper-clad plate through two-layer method |
| CN112689454A (en) * | 2020-12-23 | 2021-04-20 | 宁波今山新材料有限公司 | Method for manufacturing shielding material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0474054B1 (en) * | 1990-08-27 | 1995-12-06 | E.I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| JPH06192419A (en) * | 1992-12-25 | 1994-07-12 | Shin Etsu Chem Co Ltd | Production of polyimide film |
| JP3523952B2 (en) * | 1995-12-26 | 2004-04-26 | 日東電工株式会社 | Polyimide-metal foil composite film |
| TW526223B (en) * | 1999-10-18 | 2003-04-01 | Nippon Mektron Kk | Novel polyimide copolymer and metal laminate using the same |
-
2004
- 2004-12-07 CN CNB2004100971204A patent/CN1305933C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103145985A (en) * | 2012-12-09 | 2013-06-12 | 上海飞凯光电材料股份有限公司 | Preparation of polyimide resin and application in high-temperature-resistant optical fiber coatings thereof |
| CN103219067A (en) * | 2012-12-22 | 2013-07-24 | 西安交通大学 | Anisotropic conducting film based on carbon nano tube array and preparation method thereof |
| CN105665250A (en) * | 2016-01-28 | 2016-06-15 | 深圳市弘海电子材料技术有限公司 | Production line for preparing flexible non-adhesive polyimide copper-clad plate through two-layer method |
| CN105665250B (en) * | 2016-01-28 | 2018-11-23 | 深圳市弘海电子材料技术有限公司 | Two layers of method prepares the flexible production line without glue polyimide copper clad lamination |
| CN112689454A (en) * | 2020-12-23 | 2021-04-20 | 宁波今山新材料有限公司 | Method for manufacturing shielding material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1305933C (en) | 2007-03-21 |
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