CN104704025A - Process for manufacturing conductive polyimide film - Google Patents

Process for manufacturing conductive polyimide film Download PDF

Info

Publication number
CN104704025A
CN104704025A CN201380052550.1A CN201380052550A CN104704025A CN 104704025 A CN104704025 A CN 104704025A CN 201380052550 A CN201380052550 A CN 201380052550A CN 104704025 A CN104704025 A CN 104704025A
Authority
CN
China
Prior art keywords
electroconductibility
polyimide film
manufacture method
polyamic acid
mole
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.)
Pending
Application number
CN201380052550.1A
Other languages
Chinese (zh)
Inventor
奥聪志
柳田正美
伊藤卓
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kaneka Corp
Original Assignee
Kaneka Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kaneka Corp filed Critical Kaneka Corp
Publication of CN104704025A publication Critical patent/CN104704025A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

According to the present invention, a conductive polyimide film which exhibits excellent film strength and a desired resistivity can be manufactured with good productivity by subjecting a coating to drying and imidization, said coating comprising (A) a polyamic acid obtained by reacting a tetracarboxylic dianhydride component that contains pyromellitic dianhydride with a diamine component that contains a dimamine having three or more aromatic rings in one molecule, (B) a conductivity -imparting agent, and (C) an imidization accelerator.

Description

The manufacture method of electroconductibility polyimide film
Technical field
The present invention relates to the manufacture method of electroconductibility polyimide film.
Background technology
Polyimide film owing to having high mechanical strength, thermotolerance, reagent resistance etc., so be practical in the field widely from aerospace field to field of electronic materials.In addition, this polyimide film is given to the electroconductibility polyimide film of electroconductibility, replacement material as metal series electron material is useful, is particularly suitable for the electrode materials of battery, electromagnetic shielding material, electrostatic adhesion film, static inhibitor, image processing system parts, electronics etc.
Electroconductibility polyimide film is manufactured by following operation.
(1) will the polyamic acid solution curtain coating of conductivity imparting agent be dispersed with on supporter, form the operation of film,
(2) carry out being vaporized of solvent, remove and the operation of imidization.
In the past, in polar organic solvent after disperse black carbon, interpolation tetracarboxylic dianhydride and diamine component make it react and make polyamic acid solution, make its imidization, but the dispersiveness that there is carbon black are low, easily cause the problem of the cohesion of carbon black.
Therefore, such as, propose in patent documentation 1 by by tensio-active agent and carbon black dispersion after polyamic acid diluting soln, interpolation tetracarboxylic dianhydride and diamine component make it react, thus the method that carbon black when suppressing polymerization condenses, carry out hot-imide in embodiment and obtain semiconductive polyimide band.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2007-41214 publication
Summary of the invention
For hot-imide method, above-mentioned operation (2) required time manufacturing polyimide film is extremely long-time, has the trend of producing rate variance.
On the other hand, when making electroconductibility polyimide film by chemical imidization legal system, problem specific to the chemical imidization method that when there is imidization, drying process, carbon black re-unites, needs the improvement being suitable for chemical imidization method.
Further, sometimes film toughness is caused to reduce because of the carbon black contained by film inside.The reduction of film toughness not only causes the reduction of productivity, and causes the weather resistance as the replacement material of metal series electron material to reduce, therefore not preferred.
Therefore, the present invention is to provide a kind of productivity can manufacture film toughness excellence well and have the method for the electroconductibility polyimide film of desired resistivity.
The present inventor etc. are in view of repeatedly furtheing investigate above-mentioned aspect, result obtains following opinion: if using containing as tetracarboxylic dianhydride equal benzene tertacarbonic acid's dianhydride, there is the material of the diamines of more than 3 aromatic nucleus in a part of diamine compound, electroconductibility polyimide film is made by chemical imidization legal system, then can be controlled to no less than the low-resistivity desired by hot-imide method, therefore time of drying is the short period of time, productivity can manufacture electroconductibility polyimide film well.Further, find that the electroconductibility polyimide film obtained also has film toughness, thus complete the present invention.
Namely, the present invention relates to the manufacture method of electroconductibility polyimide film, it is characterized in that, it is the manufacture method of the electroconductibility polyimide film containing conductivity imparting agent and polyimide resin, by the dried coating film containing (A) polyamic acid, (B) conductivity imparting agent and (C) imidization promotor and imidization, should (A) polyamic acid be make the tetracarboxylic dianhydride's composition containing equal benzene tertacarbonic acid's dianhydride and react containing the diamine compound composition in a part with the diamines of more than 3 aromatic nucleus.
In the manufacture method of electroconductibility polyimide film of the present invention, the diamines in preferred above-mentioned a part with more than 3 aromatic nucleus has the structure that in following general formula (1) ~ (6), any one represents in molecule.
(part for the aromatic nucleus in general formula (1) ~ (6) can be replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl or phenoxy group.)
In the manufacture method of electroconductibility polyimide film of the present invention, the diamines in preferred above-mentioned a part with more than 3 aromatic nucleus is the compound that following general formula (7) represents.
(in general formula (7), Ar represents aromatic nucleus.X is for being selected from O, Direct Bonding, CO, C (CH 3) 2, S, SO 2in any one, can be all identical in a part, also can part or all be different.n≥2。In addition, a part of Ar can be replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl or phenoxy group, can be all identical in a part, also can part or all difference.)
In the manufacture method of electroconductibility polyimide film of the present invention, the diamines in preferred above-mentioned a part with more than 3 aromatic nucleus is at least one in the compound that is selected from following chemical formula (8) ~ (16) and represents.
In the manufacture method of electroconductibility polyimide film of the present invention, the content of preferred above-mentioned equal benzene tertacarbonic acid's dianhydride is 50 ~ 100 % by mole in above-mentioned tetracarboxylic dianhydride's composition 100 % by mole, and/or the content in above-mentioned a part with the diamines of more than 3 aromatic nucleus is 50 ~ 100 % by mole in above-mentioned diamine compound composition 100 % by mole.
In the manufacture method of electroconductibility polyimide film of the present invention, preferably above-mentioned (B) conductivity imparting agent contains carbon electroconductive particle.
In the manufacture method of electroconductibility polyimide film of the present invention, preferably the content of above-mentioned (B) conductivity imparting agent is 1 ~ 50 weight part relative to above-mentioned (A) polyamic acid 100 weight part.
In the manufacture method of electroconductibility polyimide film of the present invention, preferably above-mentioned (C) imidization promotor contains catalyzer and chemical dehydrator.
In the manufacture method of electroconductibility polyimide film of the present invention, preferably the usage quantity of the catalyzer of above-mentioned (C) imidization promotor relative to the amido acid 1 mole in above-mentioned (A) polyamic acid in the scope of 0.1 ~ 4.0 molar equivalent.
In the manufacture method of electroconductibility polyimide film of the present invention, preferably the usage quantity of the chemical dehydrator of above-mentioned (C) imidization promotor relative to the amido acid 1 mole in above-mentioned (A) polyamic acid in the scope of 1.0 ~ 5.0 molar equivalents.
In the manufacture method of electroconductibility polyimide film of the present invention, the thickness of electroconductibility polyimide film can be the scope of 1 ~ 100 μm.
In the manufacture method of electroconductibility polyimide film of the present invention, the volume specific resistance of the thickness direction of preferred electroconductibility polyimide film is 1.0 × 10 -1~ 1.0 × 10 2in the scope of Ω cm and/or surface resistivity 1.0 × 10 1~ 1.0 × 10 4in the scope of Ω/.
In the manufacture method of electroconductibility polyimide film of the present invention, anti tear propagation resistance (R, unit: the g/mm) value of preferred electroconductibility polyimide film 120 ~ 300 scope.
Manufacturing method according to the invention, film toughness is excellent, and the resistivity of the electroconductibility polyimide film obtained desirably can be adjusted in the same manner as hot-imide method.The time of drying of this manufacture method is the short period of time, therefore, it is possible to the miniaturization of implement device, the high speed of running speed, productivity is excellent.
Embodiment
An embodiment of the invention are described as follows, the present invention is not limited thereto.
The feature of the polyamic acid used in method for making of the present invention is, react by making diamine compound composition and tetracarboxylic dianhydride's composition and obtain, as tetracarboxylic dianhydride's composition, equal benzene tertacarbonic acid's dianhydride is necessary, as diamine compound composition, the diamines in a part with more than 3 aromatic nucleus is necessary.
As tetracarboxylic dianhydride's composition, except equal benzene tertacarbonic acid's dianhydride, can also and use other tetracarboxylic dianhydrides.Specifically, such as, 3 can be enumerated, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen O-phthalic acid dianhydride, two (3, the 4-dicarboxyphenyi) propane dianhydride of 2,2-, 3,4,9,10-perylenetetracarboxylic dianhydride, two (3,4-dicarboxyphenyi) propane dianhydride, two (2,3-dicarboxyphenyi) the ethane dianhydride of 1,1-, two (3,4-dicarboxyphenyi) the ethane dianhydride of 1,1-, two (2,3-dicarboxyphenyi) methane dianhydride, two (3,4-dicarboxyphenyi) ethane dianhydride, the two O-phthalic acid dianhydride of oxygen, two (3,4-dicarboxyphenyi) sulfone dianhydride, TOPOT 2,2′ p phenylenebis (trimellitic acid monoester anhydride), ethylenebis (trimellitic acid monoester anhydride), dihydroxyphenyl propane two (trimellitic acid monoester anhydride) and their part are by halogen, alkyl, haloalkyl, alkoxyl group, phenyl, the derivative etc. that phenoxy group etc. replace.
In these tetracarboxylic dianhydrides, easily obtain from the viewpoint of industrial, can preferably and with 3,3 ', 4,4 '-phenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-oxygen O-phthalic acid dianhydride.
They only can use one, also can combine two or more and use.
As diamine compound composition, it is characterized in that, containing the diamines of aromatic nucleus in a part with more than 3.
In the present invention, aromatic nucleus refers to the ring-type unsaturation of organic compound.The polycycle aromatic nucleus that the monocyclic aromatic nucleus of four ~ seven-membered ring and multiple monocycle condense is had in the ring-type unsaturation of organic compound.In the present invention, as aromatic nucleus, preferred example, can enumerate the benzene of monocyclic aromatic nucleus, the naphthalene of polycycle aromatic nucleus, anthracene, particularly preferably benzene.If have the diamines of these aromatic nucleus, then can carry out the synthesis of polyimide swimmingly.
The diamines used in the present invention is the diamines in a part with more than 3 aromatic nucleus, but the upper limit of the number of the aromatic nucleus of every a part is preferably 10, is more preferably 6.If more than 10, the synthesis of polyimide sometimes can not be carried out swimmingly.If be less than 3, then can not embody desired resistivity.
There is the diamines of more than 3 aromatic nucleus, at least containing the structure that any one in following general formula (1) ~ (6) represents in preferred molecule in a part.
Should illustrate, a part for the aromatic nucleus of above-mentioned general formula (1) ~ (6) can be replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl or phenoxy group.
As long as containing the structure that in above-mentioned general formula (1) ~ (6), any one represents, then the film strength finally obtained is excellent.
As have in structure that above-mentioned general formula (1) ~ (6) represent any one, the diamines in a part with more than 3 aromatic nucleus, it can be straight chain type, also can be branched chain type, be preferably the compound that following general formula (7) represents.
In above-mentioned general formula (7), Ar represents aromatic nucleus.X is for being selected from O, Direct Bonding, CO, C (CH 3) 2, S, SO 2in any one, can be all identical in a part, also can part or all be different.n≥2。
In addition, a part of Ar can be replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl or phenoxy group, can be all identical in a part, also can part or all difference.
As the preferred diamines in a part with more than 3 aromatic nucleus, compound and their derivative that following chemical formula (8) ~ (16) represent can be illustrated.
Here, as derivative, the compound that the part can enumerating the structural formula of above-mentioned general formula (8) ~ (16) is replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl, phenoxy group etc.
In addition to the above compounds, two { 4-(4-amino-benzene oxygen) phenyl } sulfone, two { 4-(3-amino-benzene oxygen) phenyl } sulfone etc. can also preferably be used.
The diamines in a part with more than 3 aromatic nucleus can be used alone, and also can use multiple.
In diamine compound composition, as long as in the scope not damaging effect of the present invention, just can be used together in a part the diamines with 1 or 2 aromatic nucleus.Specifically, such as, can enumerate 4,4 '-oxygen pentanoic, 4,4 '-diamino-diphenyl isopropyl alkane, 4,4 '-diaminodiphenyl-methane, p-diaminodiphenyl, 3,3 '-dichlorobenzidine, 3,3 '-tolidine, 2,2 '-tolidine, 3,3 '-dimethoxy benzidine, 2,2 '-dimethoxy benzidine, 4,4 '-diamino diphenyl sulfide, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 3,3 '-oxygen pentanoic, 3,4 '-oxygen pentanoic, 1,5-diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino-diphenyl ethyl phosphine oxide, 4,4 '-diamino-diphenyl N-methylamine, 4,4 '-diamino-diphenyl N-phenyl amine, Isosorbide-5-Nitrae-diaminobenzene (Ursol D), 1,3-diaminobenzene, 1,2-diaminobenzene, 3,3 '-diaminobenzophenone, 4,4 '-diaminobenzophenone and their part are by halogen, alkyl, haloalkyl, alkoxyl group, phenyl, the derivative etc. that phenoxy group etc. replace and obtain.
In these diamines, easily obtain from the viewpoint of industrial, can preferably also with 4,4 '-oxygen pentanoic, 4,4 '-diamino-diphenyl isopropyl alkane, Isosorbide-5-Nitrae-diaminobenzene.
In the present invention, the content of equal benzene tertacarbonic acid's dianhydride is not particularly limited, excellent and there is the electroconductibility polyimide film of high conductivity from the viewpoint of obtaining film toughness, preferably in the total mole number 100 % by mole of tetracarboxylic dianhydride's composition, contain 50 ~ 100 % by mole, more preferably containing 70 ~ 100 % by mole.
In the present invention, there is in a part the content of the diamines of more than 3 aromatic nucleus, be not particularly limited, excellent and there is the electroconductibility polyimide film of high conductivity from the viewpoint of obtaining film toughness, preferably containing 50 ~ 100 % by mole in the total mole number 100 % by mole of diamine compound composition, more preferably containing 70 ~ 100 % by mole.
In the present invention, the diamines preferably all in benzene tertacarbonic acid's dianhydride or a part with more than 3 aromatic nucleus is above-mentioned preferred content.As long as either party is above-mentioned preferred content, just easily obtain film toughness excellent and there is the electroconductibility polyimide film of high conductivity.From the viewpoint of film toughness and excellent electric conductivity, more preferably two sides are the situation of above-mentioned preferred content.
As the manufacture of polyamic acid, known all methods can be used, usually as follows to manufacture: tetracarboxylic dianhydride and diamine compound are dissolved in organic solvent with equimolar amount in fact, under the temperature condition controlled, carry out stirring until above-mentioned tetracarboxylic dianhydride terminated with being polymerized of diamine compound.
For the synthesis of the preferred solvent of polyamic acid, as long as the solvent dissolving polyamic acid just can use arbitrary solvent, but preferred amide series solvent and N, dinethylformamide, N,N-dimethylacetamide, METHYLPYRROLIDONE etc., wherein, particularly preferably can use N, dinethylformamide, N,N-dimethylacetamide.They can be used alone, and also can be mixtures of more than two kinds.
The usual preferably 5 ~ 35wt% of polyamic acid solution, more preferably obtains with the concentration of 10 ~ 30wt%.When concentration for this scope, suitable molecular weight and soltion viscosity can be obtained.
As polymerization process, the method that can use all known methods and their combinations are obtained.The feature of the polymerization process in the manufacture of polyamic acid is the order of addition of monomer whose, by controlling this monomer order of addition, can control each physical property of obtained polyimide.Therefore, in the present invention, the polymerization of polyamic acid can use the addition means of any monomer.Representatively polymerization process, can enumerate following method.That is, such as the following method.
1) diamine compound is dissolved in organic polar solvent, makes the tetracarboxylic dianhydride of first-class with its essence mole react the method for carrying out being polymerized.
2) make tetracarboxylic dianhydride and react in organic polar solvent with the diamine compound that it is in a ratio of too small molar weight, obtaining the prepolymer at two ends with anhydride group.Then, in whole operation, be essentially equimolar mode with tetracarboxylic dianhydride with diamine compound and use diamine compound to carry out the method for being polymerized.
3) make tetracarboxylic dianhydride and react in organic polar solvent with the diamine compound that it is in a ratio of excess molar amounts, obtaining, at two ends, there is amino prepolymer.Then, after adding diamine compound wherein, in whole operation, be essentially equimolar mode with tetracarboxylic dianhydride with diamine compound and use tetracarboxylic dianhydride to carry out the method for being polymerized.
4) tetracarboxylic dianhydride dissolved and/or be dispersed in after in organic polar solvent, using diamine compound to carry out the method for being polymerized to be essentially equimolar mode.
5) make the mixture of equimolar in fact tetracarboxylic dianhydride and diamine compound in organic polar solvent, react the method for carrying out being polymerized.
These methods can be used alone, and also can use by incorporating aspects.
The conductivity imparting agent used in method for making of the present invention, be not particularly limited, as long as the electroconductive stuffing that so-called filler system conductive resin composition can contain, then can use known material, such as, aluminum particulate, SUS particle, carbon electroconductive particle, silver particles, gold particle, copper particle, titanium particle, alloy particle etc. can be enumerated.Wherein, the reasons such as lightness that is little from proportion, conductive film is easy, can preferably use carbon electroconductive particle.In carbon electroconductive particle, can enumerate that Ketjen black, acetylene black, Audit For Process are black, carbon nanotube etc., higher from the electroconductibility of material itself, the reason that can obtain desired high conductivity with a small amount of addition relative to resin is set out, and particularly preferably uses Ketjen black, carbon nanotube.
Conductivity imparting agent preferably contains 1 ~ 50 weight part, more preferably 5 ~ 20 weight parts relative to polyamic acid 100 weight part.If be less than 1 weight part, then electroconductibility reduces, and damages the function as conductive film sometimes, if contrary to 50 weight parts, then the electroconductibility film strength obtained reduces, and operation sometimes becomes difficulty.
The Composite of polyamic acid and conductivity imparting agent, that is, be dispersed with the preparation of the polyamic acid solution of conductivity imparting agent, such as, can enumerate such as the following method, can use any method.
1. before polymerization or midway add the method for conductivity imparting agent to polymerization liquid,
2., after polymerization terminates, use 3 rollers etc. by method mixing for conductivity imparting agent,
3. prepare the dispersion liquid containing conductivity imparting agent, be mixed into polyamic acid solution
From the viewpoint of the Pollution restraint of the production line by make use of conductivity imparting agent to minimum, preferably the dispersion liquid containing conductivity imparting agent is mixed into the method in polyamic acid solution, particularly in the method being about to the forward slip value manufacturing film.When preparing the dispersion liquid containing conductivity imparting agent, preferably use the solvent identical with the polymer solvent of polyamic acid.Disperse well to make conductivity imparting agent and make dispersion state stabilization, dispersion agent, tackifier etc. can be used in the scope not affecting film physical property.Easily stably disperse from the viewpoint of conductivity imparting agent without cohesion, preferably a small amount of interpolation as the polyamic acid solution of the precursor of polyimide as dispersion agent.
Above-mentioned Composite, preferably uses ball mill, ball mill, sand mill, colloidal mill, micronizer mill, roller mill etc.If utilize ball mill, the methods such as ball mill are disperseed in the mode becoming the liquid state with mobility, then, in membranization operation, the operation being dispersed with the polyamic acid solution of conductivity imparting agent becomes good.The media diameters used in ball mill, ball mill, is not particularly limited, preferred below 10mm.
For the object of various characteristics improving the film such as slipperiness, sliding, heat conductivity, corona resistance, ring stiffness (loopstiffness) of electroconductibility polyimide film obtained, filler can be used.As filler, any material can be used, as preferred example, silicon-dioxide, titanium oxide, aluminum oxide, silicon nitride, boron nitride, secondary calcium phosphate, calcium phosphate, mica etc. can be enumerated.
The particle diameter of filler is decided by the kind of the filler of membrane property to be modified and interpolation, so there is no be particularly limited to, average particle diameter preferably 0.05 ~ 100 μm, more preferably 0.1 ~ 75 μm, preferably 0.1 ~ 50 μm further, particularly preferably 0.1 ~ 25 μm.If particle diameter is lower than this scope, then modified effect is difficult to embody sometimes, if exceed this scope, then sometimes greatly damage superficiality, film toughness significantly reduces.
The interpolation number of filler, also by decisions such as membrane property to be modified, packing material sizes, so there is no be particularly limited to.Usually the addition of filler is relative to polyimide 100 weight part preferably 0.01 ~ 100 weight part, is more preferably 0.01 ~ 90 weight part, more preferably 0.02 ~ 80 weight part.If filler addition is lower than this scope, then the modified effect sometimes brought by filler is difficult to embody, if exceed this scope, then film toughness is greatly impaired sometimes.
The addition means of filler similarly can apply above-mentioned Composite dispersing method, together can add, also can add in addition when the Composite dispersion of conducting imparting agent.
Method for making of the present invention, by using the chemical imidization method of imidization promotor to make above-mentioned polyamic acid be converted into polyimide, the therefore drying of short period of time, productivity is excellent.
Imidization promotor can contain catalyzer and chemical dehydrator, can also contain solvent in addition to these.Solvent is particularly preferably identical type with the solvent contained by polyamic acid solution.
Preferably tertiary amine compound can be used in catalyzer.As particularly preferred compound, quinoline, isoquinoline 99.9,3,5-lutidine, 3,5-parvolines, α-methylpyridine, beta-picoline, γ-picoline etc. can be enumerated.These compounds, can be used alone, and also can use as mixture of more than two kinds.
As the usage quantity of catalyzer, relative to the amido acid in polyamic acid 1 mole preferably 0.1 ~ 4.0 molar equivalent, more preferably 0.3 ~ 3.0 molar equivalent, further preferred 0.5 ~ 2.0 molar equivalent.If be less than 0.1 molar equivalent, then the effect as catalyzer becomes insufficient, and the problem of insufficient the carrying out of imidization and film toughness reduction occurs sometimes.On the other hand, even if more than 4.0 molar equivalents, also almost can not get the effect brought by increase addition, and be also difficult to solvent is evaporated in a series of heat treated, remaining quantitative change is many, and the film toughness sometimes obtained still reduces.
Chemical dehydrator is not particularly limited, such as, suitably can use aliphatic anhydride, aromatic anhydride, halogen-lower fatty acid anhydride etc.These can be used alone, and can use as mixture of more than two kinds.In above-mentioned chemical dehydrator, as particularly preferred compound, diacetyl oxide, propionic anhydride can be enumerated.These compounds can be used alone as described above or use as mixture of more than two kinds.
As the usage quantity of chemical dehydrator, relative to the amido acid in polyamic acid 1 mole, preferably 1.0 ~ 5.0 molar equivalents, more preferably 1.2 ~ 4.0 molar equivalents, preferred 1.5 ~ 3.0 molar equivalents further.If be less than 1.0 molar equivalents, then the imidization caused by effect of chemical dehydrator does not fully carry out, and sometimes produces the problem that film toughness reduces.On the other hand, if more than 5.0 molar equivalents, then carry out imidization with the short period of time and gelation occurs, being therefore sometimes difficult to form film.
Temperature preferably less than 10 DEG C when adding from imidization promotor to polyamic acid, more preferably less than 5 DEG C, preferably less than 0 DEG C further.If reach more than the temperature of 10 DEG C, then carry out imidization with the short period of time and gelation occurs, being therefore sometimes difficult to form film.
Method for making of the present invention, by making dried coating film containing above-mentioned polyamic acid, conductivity imparting agent and imidization promotor and imidization forms electroconductibility polyimide film.
As the coating method forming film, such as, mould can be suitably adopted to be coated with the known methods such as method, spraying method, rolling method, spin-coating method, stick coating method, ink jet method, silk screen print method, slot coated method.Adopt above-mentioned arbitrary coating method etc. on the supporter such as metal drum, metal strip, carry out film, after temperature about room temperature ~ 200 DEG C obtains self-supporting desciccator diaphragm, further film is fixed, be heated to the temperature that outlet temperature is about 600 DEG C, obtain electroconductibility polyimide film.The fixing of film suitably can adopt the known methods such as pin tentering mode, cloth gripper tentering mode, roller overhanging way, and its form is not limit.
Heating temperature can suitably set, and a high side is because easily cause imidization, so can accelerate curing speed, preferred from the viewpoint of productivity.But, if temperature is too high, then likely cause thermolysis.On the other hand, if Heating temperature is too low, be then difficult to imidization, required for curing process, the time is elongated.
For heat-up time, the sufficient time for imidization and drying terminate in fact can be taked, can not limit without exception, generally suitably set the scope of about 1 ~ 600 second.
The thickness of method for making of the present invention by suitably regulating the parts by weight of the concentration of the thickness of the film on supporter, polyamic acid, conductivity imparting agent suitably to set electroconductibility polyimide film.The thickness of film is preferably 1 ~ 1000 μm.If thinner than 1 μm, then the film toughness sometimes finally obtained is not enough, if thicker than 1000 μm, then sometimes flows on supporter.The thickness of the electroconductibility polyimide film finally obtained preferably 1 ~ 100 μm, is more preferably 5 ~ 50 μm.If thinner than 1 μm, then film toughness is not enough sometimes, if thick than 100 μm, then imidization drying becomes difficulty equably sometimes, mechanical characteristics produces deviation, or the easy local defect such as appearance foaming.
Method for making of the present invention, in order to the volume specific resistance of the thickness direction by the electroconductibility obtained polyimide film and surface resistivity desirably adjust, suitably can set the kind of polyimide, the kind, addition etc. of conductivity imparting agent.
The volume specific resistance of the thickness direction of electroconductibility polyimide film preferably 1.0 × 10 -1~ 1.0 × 10 2Ω cm, more preferably 1.0 × 10 -1~ 8.0 × 10 1Ω cm, further preferably 1.0 × 10 -1~ 5.0 × 10 1Ω cm.
The surface resistivity of electroconductibility polyimide film preferably 1.0 × 10 1~ 1.0 × 10 4Ω/, more preferably 1.0 × 10 1~ 5.0 × 10 3Ω/, further preferably 1.0 × 10 1~ 3.0 × 10 3Ω/.
With regard to the electroconductibility polyimide film obtained by method for making of the present invention, can stablize from the view point of film carrying during masking and carry out, anti tear propagation resistance (R, unit: the g/mm) value of preferred electroconductibility polyimide film 130 ~ 300 scope.If the value of R is in preferred scope, can judge that there is sufficient film toughness.On the other hand, when the value of R is less than 130, film toughness is not enough, therefore sometimes not only causes the reduction of productivity, and causes the reduction of weather resistance.From the view point of productivity and weather resistance, more preferably R value 160 ~ 300 scope.
The electroconductibility polyimide film obtained in manufacture method of the present invention, re-uniting of conductivity imparting agent is inhibited, and uses minimal conductivity imparting agent just to have desired volume specific resistance and surface resistivity.Therefore, it is possible to stably use for a long time in the electrode materials, electromagnetic shielding material, electrostatic adhesion film, static inhibitor, image processing system parts, electronics etc. of metal series electron material, battery, can preferably adopt.
Embodiment
For the present invention, be described in more detail effect based on embodiment and comparative example, but the present invention is not limited thereto.Those skilled in the art without departing from the scope of the invention, can carry out various change, correction and change.
The evaluation of the volume specific resistance of the electroconductibility polyimide film obtained in embodiment and comparative example, surface resistivity and film toughness, carries out measuring and evaluating as follows.
(volume specific resistance)
The electroconductibility polyimide film obtained is cut into the size of 15mm, the region of the central part 10mm on two sides adopts sputtering method to form gold thin film.Make Copper Foil closely sealed with gold thin film respectively by the pressurization of 1MPa, be determined at current potential V when to flow through electric current I between 2 Copper Foils, using measured value V/I as volume specific resistance.The mensuration of resistance value uses LCR HiTESTER (3522-50, Zhi Electric Co., Ltd system).
(surface resistivity)
Measure and use LORESTA-GP (MCP-T610, Mitsubishi ChemicalAnalytech Co., Ltd. system), 4 probe detectors are crimped on obtained electroconductibility polyimide film surface measurements surface resistivity.
If the value of volume specific resistance is 1.0 × 10 -1~ 1.0 × 10 2the scope of Ω cm, and the value of surface resistivity is 1.0 × 10 1~ 1.0 × 10 4the scope of Ω/, is judged as resistance excellence (zero), if volume specific resistance, both surface resistivities exceed this scope, is evaluated as resistance difference (×).
(evaluation of film toughness)
The anti tear propagation resistance R of the electroconductibility polyimide film obtained measures according to JIS K 7128 pants type method of Tearing.If anti tear propagation resistance (R, unit: g/mm) value is the scope of 120 ~ 300, is then judged as film toughness excellence (zero), if be less than 120, is then evaluated as film toughness difference (×).
(embodiment 1)
As the organic solvent of polymerization, use N, dinethylformamide is (following, DMF), use equal benzene tertacarbonic acid's dianhydride (following, PMDA) 100 % by mole as tetracarboxylic dianhydride, use in 1 molecule and there are 1 of 3 aromatic nucleus, two (4-amino-benzene oxygen) benzene of 3-is (following, TPE-R) 100 % by mole as diamine compound, the mode be essentially etc. % by mole with tetracarboxylic dianhydride and diamine compound is added in reactive tank and is stirred, polymerization, synthesizing polyamides acid solution thus.Now, with the solid component concentration of the polyamic acid solution obtained be 15 % by weight, viscosity is 300 ~ 400Pas (Dong Ji Industrial Co., Ltd E type viscometer; TVE-22H, the value of 23 DEG C) mode synthesize.
Polyamic acid solution 10 weight part obtained, Ketjen black (ECP600JD, Lion Co., Ltd. system) 1 weight part and DMF20 weight part ball mill are implemented dispersion treatment, obtains carbon dispersion liquid.Dispersion uses the zirconia ball of 5mm φ, under rotating speed 600rpm, sets the treatment time of 30 minutes.
In addition, carbon dispersion liquid 100 weight part obtained and polyamic acid solution 183 weight part obtained are mixed, obtains carbon dispersed polyamic acid solution.Now, relative to polyamic acid 100 weight part, Ketjen black is 10 weight parts.
Add to above-mentioned carbon dispersed polyamic acid solution 100g the imidization promotor that is made up of isoquinoline 99.9 11.4g, diacetyl oxide 12g and DMF16.6g and mix, by gains with final thickness be 25 μm mode and with 40cm width curtain coating on aluminium foil, carry out drying 216 seconds at 120 DEG C, obtain self-supporting film.After self-supporting film is peeled off from aluminium foil, be fixed on needle plate, 250 DEG C of drying 200 seconds, then, 400 DEG C of dryings 64 seconds, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(embodiment 2)
Use DMF as the organic solvent of polymerization, use PMDA100 % by mole as tetracarboxylic dianhydride, use in 1 molecule and there are 2 of 4 aromatic nucleus, 2 '-bis-{ 4-(4-amino-benzene oxygen) phenyl } propane is (following, BAPP) 100 % by mole as diamine compound, the mode be essentially etc. % by mole with tetracarboxylic dianhydride and diamine compound is added in reactive tank and is stirred, polymerization, synthesizing polyamides acid solution thus.Now, with the solid component concentration of the polyamic acid solution obtained be 15 % by weight, viscosity is 300 ~ 400Pas (Dong Ji Industrial Co., Ltd E type viscometer; TVE-22H, the value of 23 DEG C) mode synthesize.
Polyamic acid solution 10 weight part obtained, Ketjen black (ECP600JD, Lion Co., Ltd. system) 1 weight part and DMF20 weight part ball mill are implemented dispersion treatment, obtains carbon dispersion liquid.Dispersion uses the zirconia ball of 5mm φ, sets the treatment time of 30 minutes under rotating speed 600rpm.
Further, carbon dispersion liquid 100 weight part obtained and polyamic acid solution 183 weight part obtained are mixed, obtains carbon dispersed polyamic acid solution.Now, relative to polyamic acid 100 weight part, Ketjen black is 10 weight parts.
Add to above-mentioned carbon dispersed polyamic acid solution 100g the imidization promotor that is made up of isoquinoline 99.9 9.3g, diacetyl oxide 9.7g and DMF21g and mix, by gains with final thickness be 25 μm mode and with 40cm width curtain coating on aluminium foil, carry out drying 216 seconds at 120 DEG C, obtain self-supporting film.After self-supporting film is peeled off from aluminium foil, be fixed on needle plate, 250 DEG C of dryings 200 seconds, then carry out drying 64 seconds at 400 DEG C, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(embodiment 3)
Except final thickness is 12.5 μm, obtain electroconductibility polyimide film similarly to Example 2.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(embodiment 4)
Use DMF as the organic solvent of polymerization; use PMDA100 % by mole as tetracarboxylic dianhydride; use in 1 molecule and there are 1 of 5 aromatic nucleus; two { 4-(3-amino-benzene oxygen) benzoyl } benzene of 3-is (following; BABB) 100 % by mole as diamine compound; the mode be essentially etc. % by mole with tetracarboxylic dianhydride and diamine compound is added in reactive tank and is carried out stirring, being polymerized, synthesizing polyamides acid solution thus.Now, be 15 % by weight with the solid component concentration of the polyamic acid solution obtained, viscosity is 300 ~ 400Pas (Dong Ji Industrial Co., Ltd E type viscometer; TVE-22H, the value of 23 DEG C) mode synthesize.
Polyamic acid solution 10 weight part obtained, Ketjen black (ECP600JD, Lion Co., Ltd. system) 1 weight part and DMF20 weight part ball mill are implemented dispersion treatment, obtains carbon dispersion liquid.Dispersion uses the zirconia ball of 5mm φ, sets the treatment time of 30 minutes under rotating speed 600rpm.
Further, carbon dispersion liquid 100 weight part obtained and polyamic acid solution 183 weight part obtained are mixed, obtains carbon dispersed polyamic acid solution.Now, relative to polyamic acid 100 weight part, Ketjen black is 10 weight parts.
Add relative to above-mentioned carbon dispersed polyamic acid solution 100g the imidization promotor that is made up of isoquinoline 99.9 8.1g, diacetyl oxide 8.5g and DMF23.4g and mix, by gains with final thickness be 25 μm mode and with 40cm width curtain coating on aluminium foil, carry out drying 216 seconds at 120 DEG C, obtain self-supporting film.After self-supporting film is peeled off from aluminium foil, be fixed on needle plate, 250 DEG C of dryings 200 seconds, then carry out drying 64 seconds at 400 DEG C, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(embodiment 5)
Use DMF as the organic solvent of polymerization, use PMDA50 % by mole, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride 50 % by mole is as tetracarboxylic dianhydride, use in 1 molecule and there are 4 of 2 aromatic nucleus, 4 '-oxygen pentanoic is (following, ODA) 50 % by mole, there is BAPP50 % by mole of 4 aromatic nucleus as diamine compound in 1 molecule, tetracarboxylic dianhydride and diamine compound add in reactive tank in the mode to be essentially etc. % by mole and carry out stirring, being polymerized, synthesizing polyamides acid solution thus.Now, with the solid component concentration of the polyamic acid solution obtained be 15 % by weight, viscosity is 300 ~ 400Pas (Dong Ji Industrial Co., Ltd E type viscometer; TVE-22H, the value of 23 DEG C) mode synthesize.
Polyamic acid solution 10 weight part obtained, Ketjen black (ECP600JD, Lion Co., Ltd. system) 1 weight part and DMF20 weight part ball mill are implemented dispersion treatment, obtains carbon dispersion liquid.Dispersion uses the zirconia ball of 5mm φ, sets the treatment time of 30 minutes under rotating speed 600rpm.
Further, carbon dispersion liquid 100 weight part obtained and polyamic acid solution 183 weight part obtained are mixed, obtains carbon dispersed polyamic acid solution.Now, relative to polyamic acid 100 weight part, Ketjen black is 10 weight parts.
Add relative to above-mentioned carbon dispersed polyamic acid solution 100g the imidization promotor that is made up of isoquinoline 99.9 10.1g, diacetyl oxide 10.6g and DMF19.3g and mix, by gains with final thickness be 25 μm mode and with 40cm width curtain coating on aluminium foil, carry out drying 216 seconds at 120 DEG C, obtain self-supporting film.After self-supporting film is peeled off from aluminium foil, be fixed on needle plate, 250 DEG C of dryings 200 seconds, then carry out drying 64 seconds at 400 DEG C, obtain electroconductibility polyimide film.To the electroconductibility polyimide film obtained, carry out the mensuration of volume specific resistance, surface resistivity, film toughness.
(embodiment 6)
In embodiment 2, use 3,5-parvoline to replace isoquinoline 99.9, in addition, similarly obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(comparative example 1)
Use DMF as the organic solvent of polymerization, use PMDA100 % by mole as tetracarboxylic dianhydride, use the Ursol D in 1 molecule with an aromatic nucleus (following, p-PDA) 100 % by mole as diamine compound, tetracarboxylic dianhydride and diamine compound add in reactive tank in the mode to be essentially etc. % by mole and carry out stirring, being polymerized, synthesizing polyamides acid solution thus.Now, be 15 % by weight with the solid component concentration of the polyamic acid solution obtained, viscosity is 300 ~ 400Pas (Dong Ji Industrial Co., Ltd E type viscometer; TVE-22H, the value of 23 DEG C) mode synthesize.
Polyamic acid solution 10 weight part obtained, Ketjen black (ECP600JD, Lion Co., Ltd. system) 1 weight part and DMF20 weight part ball mill are implemented dispersion treatment, obtains carbon dispersion liquid.Dispersion uses the zirconia ball of 5mm φ, sets the treatment time of 30 minutes under rotating speed 600rpm.
Further, carbon dispersion liquid 100 weight part obtained and polyamic acid solution 183 weight part obtained are mixed, obtains carbon dispersed polyamic acid solution.Now, relative to polyamic acid 100 weight part, Ketjen black is 10 weight parts.
Add relative to above-mentioned carbon dispersed polyamic acid solution 100g the imidization promotor that is made up of isoquinoline 99.9 17.8g, diacetyl oxide 18.8g and DMF3.4g and mix, by gains with final thickness be 25 μm mode and with 40cm width curtain coating on aluminium foil, carry out drying 216 seconds at 120 DEG C, obtain self-supporting film.After self-supporting film is peeled off from aluminium foil, be fixed on needle plate, 250 DEG C of dryings 200 seconds, then carry out drying 64 seconds at 400 DEG C, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(comparative example 2)
Use DMF as the organic solvent of polymerization, use PMDA100 % by mole as tetracarboxylic dianhydride, 1 molecule is used to have ODA100 % by mole of 2 aromatic nucleus as diamine compound, tetracarboxylic dianhydride and diamine compound add in reactive tank in the mode to be essentially etc. % by mole and carry out stirring, being polymerized, synthesizing polyamides acid solution thus.Now, be 15 % by weight with the solid component concentration of the polyamic acid solution obtained, viscosity is 300 ~ 400Pas (Dong Ji Industrial Co., Ltd E type viscometer; TVE-22H, the value of 23 DEG C) mode synthesize.
Polyamic acid solution 10 weight part obtained, Ketjen black (ECP600JD, Lion Co., Ltd. system) 1 weight part and DMF20 weight part ball mill are implemented dispersion treatment, obtains carbon dispersion liquid.Dispersion uses the zirconia ball of 5mm φ, sets the treatment time of 30 minutes under rotating speed 600rpm.
Further, carbon dispersion liquid 100 weight part obtained and polyamic acid solution 183 weight part obtained are mixed, obtains carbon dispersed polyamic acid solution.Now, relative to polyamic acid 100 weight part, Ketjen black is 10 weight parts.
Add relative to above-mentioned carbon dispersed polyamic acid solution 100g the imidization promotor that is made up of isoquinoline 99.9 13.9g, diacetyl oxide 14.6g and DMF11.5g and mix, by gains with final thickness be 25 μm mode and with 40cm width curtain coating on aluminium foil, carry out drying 216 seconds at 120 DEG C, obtain self-supporting film.After self-supporting film is peeled off from aluminium foil, be fixed on needle plate, 250 DEG C of dryings 200 seconds, then carry out drying 64 seconds at 400 DEG C, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(comparative example 3)
The carbon dispersed polyamic acid solution 100g obtained in embodiment 2 is the mode of 25 μm with final thickness and with 40cm width curtain coating in PET film, carries out drying 600 seconds at 70 DEG C.After being peeled off from PET film by dried self-supporting film, be fixed on pin tenter, heated up with 450 seconds from 160 DEG C to 300 DEG C dry on one side, then carry out drying 180 seconds at 400 DEG C, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
(comparative example 4)
The carbon dispersed polyamic acid solution 100g obtained in comparative example 2 is the mode of 25 μm with final thickness and with 40cm width curtain coating in PET film, carries out drying 600 seconds at 70 DEG C.After being peeled off from PET film by dried self-supporting film, be fixed on pin tenter, heated up with 450 seconds from 160 DEG C to 300 DEG C dry on one side, then carry out drying in 180 seconds at 400 DEG C, obtain electroconductibility polyimide film.The volume specific resistance of the electroconductibility polyimide film obtained, surface resistivity, film toughness are measured.
The evaluation result of the film of above embodiment and comparative example is shown in table 1.
[table 1]
As shown in table 1, the resistance of the electroconductibility polyimide film obtained in embodiment 1 ~ 6, film toughness are all good, and on the other hand, the electroconductibility polyimide film obtained in comparative example 1 ~ 2 cannot get both resistance, film toughness.
In addition, embodiment 2 and comparative example 3 manufacture the electroconductibility polyimide film of identical polyimide structures respectively by the method for making of chemical imidization method, hot-imide method, but do not limit by method for making, be obtained for the electroconductibility polyimide film of equal resistance and film toughness.On the other hand, the electroconductibility polyimide film that comparative example 2 and comparative example 4 adopt chemical imidization method respectively, the method for making of hot-imide method manufactures identical polyimide structures, but the resistance of chemical imidization method is high, the electroconductibility polyimide film equal with hot-imide method can not be obtained.
Thus, known manufacture method of the present invention is effective.

Claims (13)

1. a manufacture method for electroconductibility polyimide film, is characterized in that, is the manufacture method of the electroconductibility polyimide film containing conductivity imparting agent and polyimide resin,
This manufacture method is by the dried coating film containing (A) polyamic acid, (B) conductivity imparting agent and (C) imidization promotor and imidization, and described (A) polyamic acid is that the tetracarboxylic dianhydride's composition containing equal benzene tertacarbonic acid's dianhydride is reacted with the diamine compound composition containing the diamines in a part with more than 3 aromatic nucleus.
2. the manufacture method of electroconductibility polyimide film according to claim 1, wherein, the described diamines in a part with more than 3 aromatic nucleus has the structure that in following general formula (1) ~ (6), any one represents in molecule,
A part for aromatic nucleus in general formula (1) ~ (6) can be replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl or phenoxy group.
3. the manufacture method of electroconductibility polyimide film according to claim 1 and 2, wherein, the described diamines in a part with more than 3 aromatic nucleus is the compound that following general formula (7) represents,
In general formula (7), Ar represents aromatic nucleus; X is for being selected from O, Direct Bonding, CO, C (CH 3) 2, S, SO 2in any one, can be all identical in a part, also can part or all be different; N>=2; In addition, a part of Ar can be replaced by halogen, alkyl, haloalkyl, alkoxyl group, phenyl or phenoxy group, can be all identical in a part, also can part or all difference.
4. the manufacture method of the electroconductibility polyimide film according to any one of claims 1 to 3, wherein, the described diamines in a part with more than 3 aromatic nucleus is at least one in the compound that is selected from following chemical formula (8) ~ (16) and represents
5. the manufacture method of the electroconductibility polyimide film according to any one of Claims 1 to 4, wherein, the content of described equal benzene tertacarbonic acid's dianhydride is 50 ~ 100 % by mole in described tetracarboxylic dianhydride's composition 100 % by mole, and/or the described content in a part with the diamines of more than 3 aromatic nucleus is 50 ~ 100 % by mole in described diamine compound composition 100 % by mole.
6. the manufacture method of the electroconductibility polyimide film according to any one of Claims 1 to 5, wherein, described (B) conductivity imparting agent contains carbon electroconductive particle.
7. the manufacture method of the electroconductibility polyimide film according to any one of claim 1 ~ 6, wherein, the content of described (B) conductivity imparting agent is 1 ~ 50 weight part relative to described (A) polyamic acid 100 weight part.
8. the manufacture method of the electroconductibility polyimide film according to any one of claim 1 ~ 7, wherein, described (C) imidization promotor contains catalyzer and chemical dehydrator.
9. the manufacture method of electroconductibility polyimide film according to claim 8, wherein, the usage quantity of the catalyzer of described (C) imidization promotor relative to the amido acid 1 mole in described (A) polyamic acid in the scope of 0.1 ~ 4.0 molar equivalent.
10. the manufacture method of the electroconductibility polyimide film according to any one of according to Claim 8 ~ 9, wherein, the usage quantity of the chemical dehydrator of described (C) imidization promotor relative to the amido acid 1 mole in described (A) polyamic acid in the scope of 1.0 ~ 5.0 molar equivalents.
The manufacture method of 11. electroconductibility polyimide films according to any one of claim 1 ~ 10, wherein, the thickness of electroconductibility polyimide film is the scope of 1 ~ 100 μm.
The manufacture method of 12. electroconductibility polyimide films according to any one of claim 1 ~ 11, wherein, the volume specific resistance of the thickness direction of electroconductibility polyimide film is 1.0 × 10 -1~ 1.0 × 10 2in the scope of Ω cm and/or surface resistivity 1.0 × 10 1~ 1.0 × 10 4in the scope of Ω/.
The manufacture method of 13. electroconductibility polyimide films according to any one of claim 1 ~ 12, wherein, the anti tear propagation resistance R value of electroconductibility polyimide film is in the scope of 120 ~ 300, and the unit of R is g/mm.
CN201380052550.1A 2012-10-10 2013-10-03 Process for manufacturing conductive polyimide film Pending CN104704025A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2012-225430 2012-10-10
JP2012225430 2012-10-10
PCT/JP2013/076942 WO2014057862A1 (en) 2012-10-10 2013-10-03 Process for manufacturing conductive polyimide film

Publications (1)

Publication Number Publication Date
CN104704025A true CN104704025A (en) 2015-06-10

Family

ID=50477329

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201380052550.1A Pending CN104704025A (en) 2012-10-10 2013-10-03 Process for manufacturing conductive polyimide film

Country Status (4)

Country Link
JP (1) JP6361507B2 (en)
CN (1) CN104704025A (en)
TW (1) TWI605474B (en)
WO (1) WO2014057862A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110358295A (en) * 2019-08-22 2019-10-22 深圳先进技术研究院 It is a kind of with electromagnetic shielding and the polyimide composite film of thermally conductive function and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6621248B2 (en) * 2014-06-27 2019-12-18 東京応化工業株式会社 Black composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08143665A (en) * 1994-11-22 1996-06-04 Toho Rayon Co Ltd Electrically conductive composite and its production
WO2012057302A1 (en) * 2010-10-28 2012-05-03 株式会社カネカ Process for production of electrically conductive polyimide film

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60170626A (en) * 1984-02-15 1985-09-04 Nitto Electric Ind Co Ltd Electrically conductive paste composition for electronic part
US5302652A (en) * 1992-12-15 1994-04-12 E. I. Du Pont De Nemours And Company Process for preparing a pigmented polyimide shaped article
JP2008188954A (en) * 2007-02-07 2008-08-21 Kaneka Corp Base material for single-sided metal-clad laminated sheet and manufacturing method of single-sided metal-clad laminated sheet
JP5446655B2 (en) * 2009-09-18 2014-03-19 富士ゼロックス株式会社 Polyimide polymer composition, polyimide endless belt, method for producing polyimide endless belt, belt unit, and image forming apparatus

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08143665A (en) * 1994-11-22 1996-06-04 Toho Rayon Co Ltd Electrically conductive composite and its production
WO2012057302A1 (en) * 2010-10-28 2012-05-03 株式会社カネカ Process for production of electrically conductive polyimide film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110358295A (en) * 2019-08-22 2019-10-22 深圳先进技术研究院 It is a kind of with electromagnetic shielding and the polyimide composite film of thermally conductive function and preparation method thereof

Also Published As

Publication number Publication date
TW201423769A (en) 2014-06-16
WO2014057862A1 (en) 2014-04-17
JP6361507B2 (en) 2018-07-25
TWI605474B (en) 2017-11-11
JPWO2014057862A1 (en) 2016-09-05

Similar Documents

Publication Publication Date Title
CN103180390B (en) The manufacture method of electroconductibility polyimide film
CN104823314B (en) Collector for bipolar lithium ion secondary battery and bipolar lithium ion secondary battery
CN105368048B (en) Kapton of antistatic absorption and preparation method thereof
CN108117658A (en) The preparation method of electrostatic prevention suction agglomeration imide membrane
CN101945820B (en) Conductive material and manufacturing method thereof
CN104245844B (en) The manufacture method of electric conductivity polyimide film
JP5783789B2 (en) Method for producing conductive polyimide film
CN104704025A (en) Process for manufacturing conductive polyimide film
JP5347842B2 (en) Polyimide precursor solution composition containing fine carbon fibers and polyimide film using the same
JP2003192893A (en) Polyimide resin composition, polyimide film, polyimide tube and tube for electrophotography
JP2007298692A (en) Anisotropic conductive polyimide belt and method for manufacturing the same
WO2002022740A1 (en) Polyimide resin composition and, polyimide product formed into film and intermediate transfer belt comprising the same
JP5128893B2 (en) Conductive polyimide belt
CN102030988B (en) Seamless belt and preparation method thereof
JP5810833B2 (en) Method for producing conductive polyimide film
JP2016000769A (en) Method for producing conductive polyimide film
JP2004131659A (en) Polyimide resin composition and molded polyimide article made thereof
TW201402694A (en) Seamless belt
CN108503831A (en) To form the constituent, polyimides and polyimide film of polyimides
TWI685544B (en) Composition for forming polyimide, polyimide and polyimide film
JP2003213131A (en) Polyimide resin composition, polyimide film, polyimide tubular product and tubular product for electrophotography
JP2016139040A (en) Intermediate transfer belt for image forming apparatus
JP2004094008A (en) Polyamide acid solution and semiconductive polyimide belt

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20150610