CN100580014C - Semiconductive polyimide film and process for production thereof - Google Patents

Semiconductive polyimide film and process for production thereof Download PDF

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Publication number
CN100580014C
CN100580014C CN200610138831A CN200610138831A CN100580014C CN 100580014 C CN100580014 C CN 100580014C CN 200610138831 A CN200610138831 A CN 200610138831A CN 200610138831 A CN200610138831 A CN 200610138831A CN 100580014 C CN100580014 C CN 100580014C
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film
mentioned
polyimide film
polyamic acid
mineral filler
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CN1935879A (en
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金城永泰
西川泰司
赤堀廉一
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Kaneka Corp
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Kaneka Corp
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Abstract

A polyamic acid solution and/or a polyamic acid gel film is subjected to at least one treatment selected from among addition of a semiconductive inorganic filler, addition of an electroconductivity-imparting agent, and formation of a conducting film; and then the polyamic acid contained in the resulting solution or film is subjected to imidation. The semiconductive polyimide film thus produced is well controlled in surface resistance and volume resistance with reduction in the voltage dependences of both resistances, has excellent mechanical characteristics, and realizes a high elongation.

Description

Semiconductive polyimide film and manufacture method thereof
The application is a Chinese patent application (denomination of invention: semiconductive polyimide film and manufacture method thereof, the applying date: on June 14th, 2002; Dividing an application application number 02812040.X).
Technical field
The present invention relates to be applicable to the electrode materials, electromagnetic shielding material, electrostatic adhesion of battery semiconductive polyimide film and manufacture method thereof with film, antistatic agent, image processing system parts, electron device etc.
Background technology
In the past, as the method for improvement polyimide film conductivity, the known method (, being called the 1st method) that mixed conductivity weighting agent in the polyimide is arranged for ease of illustrating.So-called above-mentioned electroconductibility weighting agent refers generally to various substrate material, is coated and gives the material of electroconductibility with conductive materials such as carbon, graphite, metallics, tin indium oxides, and promptly filler also has this character.
Yet, when heuristicing the electroconductibility improvement with above-mentioned the 1st method, produce following point.At first, resulting polyimide film, in most cases mechanical property worsens.In addition, with the electroconductibility weighting agent (filler) that above-mentioned the 1st method obtains, (resistance value is up to 10 because its resistivity is very low 3About Ω cm), so in the semi-conductivity zone, controlling resistance is difficulty very, particularly, in the reproducibility that improves surface resistivity and volume poor efficiency, be difficult to make the interior deviation of its face to diminish.And with the polyimide film that above-mentioned the 1st method obtains, the mensuration voltage-dependent of its resistivity strengthens.
As same technology, Japan openly speciallys permit communique " spy opens flat 1-146957 communique " (open day on June 8th, 1989) and discloses filler metal oxide compound fines (filler) and sooty resin combination (for ease of explanation, being called the 2nd method).
Yet above-mentioned the 2nd method is particularly suitable for the manufacturing of the telescopic semi-conducting resin composition of developer roll in a kind of electro photography image processing system of composition visualization way.That is, adopt this technology, can reach the purpose that the semi-conducting resin composition of the desirable characteristic of sleeve pipe is given full play in acquisition.In order to realize above-mentioned characteristic, it is difficult only adopting the filler of good electroconductibility or any material of sooty, and must both and usefulness.
In fact, adopt the 2nd method, because emphasis only is the adjusted volume resistance value, so, adopt this method when resin treatment is become membranaceous, be difficult to sheet resistance value is transferred to suitably.Therefore, same with above-mentioned the 1st method when the 2nd method is applied to polyimide film, the reproducibility variation of the surface resistivity of resulting polyimide film.
In addition, as the technology of improving above-mentioned the whole bag of tricks shortcoming, for example, known have Japan openly to specially permit communique " spy opens flat 8-259810 communique " (open day on October 8th, 1996) and Japan openly speciallys permit communique " spy opens flat 8-259709 communique " (open day on October 8th, 1996) disclosed method (for ease of explanation, being called the 3rd method).Adopt disclosed the 3rd method in these communiques, can give electroconductibility by the polymer blending of polyaniline and polyimide.
Yet, produce following point when adopting above-mentioned the 3rd method.At first, because the electroconductibility that polyaniline has is ionic conductivity, so its resistance value is subjected to the influence of environment big.And, in the manufacturing of polyaniline, can't determine owing to industrial sufficient productivity, so, very expensive with the blend of polymkeric substance.
In addition, as the another kind of technology different with above-mentioned the 3rd method, known for example have, Japan openly speciallys permit communique " spy opens flat 11-279437 communique " (open day on October 12nd, 1999), Japan openly speciallys permit communique " spy opens the 2000-207959 communique " (open day on July 28th, 2000) or Japan openly speciallys permit communique " spy opens the 2001-2954 communique " (open day January 9 calendar year 2001) disclosed method (for ease of explanation, being called the 4th method).Adopt disclosed the 4th method of these communiques, make the coating fluid be used to form the metal conductive oxide film, adopt this coating fluid on non-lead base material, to form conducting film and give electroconductibility.
But above-mentioned the 4th method is because only at the surface of base material formation conducting film, so the problem that exists is that its volume resistance value does not descend.
Therefore, adopt above-mentioned the whole bag of tricks, surface resistivity and volume resistance that can more accurate control polyimide film, and the voltage-dependent of resistance value but is difficult to improve its elongation and mechanical property little the time.
The content of invention
The inventor is for solving above-mentioned original variety of issue, with for control surface resistance and volume resistance well are provided, when the voltage-dependent of these resistance values reduces, the result that the polyimide film of the elongation that the realization mechanical characteristics is good, high is furtherd investigate has finished the present invention.
Promptly, in order to solve above-mentioned problem, the semiconductive polyimide film that the present invention relates to, be containing the organic solvent solution of polyamic acid as polyamic acid solution, and at polyamic acid when the partly solidified and/or dry film that obtains of part is as gel-film, at least to above-mentioned polyamic acid solution and/or gel-film, implement the interpolation of semi-conductivity mineral filler, after arbitrary operation of the interpolation of electroconductibility imparting agent and formation conducting film, polyamic acid contained in above-mentioned polyamic acid solution or the gel-film is obtained by imidization, and its formation is that the sheet resistance value that records under impressed voltage 100V is 10 8～10 13In the scope of Ω/, and the volume resistance value is 10 8～10 14In the scope of Ω cm.
In order to solve above-mentioned problem, the manufacture method of this semiconductive polyimide film that the present invention relates to comprises: the organic solvent solution that contains polyamic acid make polyamic acid solution, when making the partly solidified and/or dry film that obtains of part of polyamic acid make gel-film, to polyamic acid solution and/or gel-film, implement the interpolation of semi-conductivity mineral filler, the interpolation of electroconductibility imparting agent, and any at least electroconductibility of formation conducting film is given operation; Give back imidization operation with the electroconductibility of after above-mentioned electroconductibility is given operation, polyamic acid contained in above-mentioned polyamic acid or the gel-film being carried out imidization.
Particularly, the semiconductive polyimide film that the present invention relates to, as necessary composition, be (in other words with 85: 15～50: 50, contain the semi-conductivity mineral filler of 15～50 weight %) ratio contain the polyimide film of polyimide and semi-conductivity mineral filler, the sheet resistance value of measuring under impressed voltage 100V is 10 10Ω/～10 13In the scope of Ω/, the volume resistance value is 10 10Ω cm～10 14In the scope of Ω cm.
In addition, the manufacture method of the semiconductive polyimide film that the present invention relates to, be included in the slurry of homodisperse semi-conductivity mineral filler by polymerization, preparation contains the polyamic acid solution of semi-conductivity mineral filler, make the film making solution curtain coating on base material that contains this solution make film, this film is by heat or the chemical method manufacturing processed of imidization in addition; Or, polyamic acid solution and the homodisperse slurry of semi-conductivity mineral filler are mixed, make this mixed solution curtain coating system, film forming on base material, this film is by heat or the chemical method manufacturing processed of imidization in addition; Or, the semi-conductivity mineral filler directly is dispersed in the polyamic acid solution, make this mixed solution curtain coating, film forming on base material, this film is by heat or the chemical method method of the manufacturing processed of imidization in addition.
According to above-mentioned formation and method, can make a kind of resistance value with semi-conductivity zone, the mensuration voltage-dependent of resistance value is little, or precision is better and surface resistivity and volume resistance control easily, and the semiconductive polyimide film with good physical strength.
In addition, the semiconductive polyimide film manufacture method that the present invention relates to also is partly solidified and/or part exsiccant gel-film to be formed with coating fluid with the metal conductive oxide film flood and/or be coated with, then, residual amido acid carries out imidization, and makes this film exsiccant method.In addition, in the method, gel-film also can contain the semi-conductivity mineral filler.
By the semiconductive polyimide film that the present invention relates to that aforesaid method obtains, the sheet resistance value of measuring under impressed voltage 100V is 10 8Ω/～10 12In the scope of Ω/, and the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm.
Perhaps, the manufacture method of the semiconductive polyimide film that the present invention relates to also is that organic solvent solution that contains polyamic acid and metal conductive oxide film are formed the film making solution of using coating fluid, delays at the supporting mass upper reaches, carry out imidization, and carry out the exsiccant method.In addition, in the method, gel-film also can contain the semi-conductivity mineral filler.
According to above-mentioned formation or method, in the semi-conductivity zone, volume resistance value and sheet resistance value can precision good and control easily.Yet, resulting semiconductive polyimide film, when can reduce the voltage-dependent of above-mentioned each resistance value, the resistance value deviation in the face is also little.
The present invention reaches purpose of the present invention according to the technical scheme of the following stated.
(1). a kind of semiconductive polyimide film, this film be will contain polyamic acid organic solvent solution as polyamic acid solution, again polyamic acid is partly solidified and/or partly dry and with resulting film during as gel-film,
At least, to above-mentioned polyamic acid solution and/or gel-film, at least after any a kind of operation of the formation of the interpolation of enforcement semi-conductivity mineral filler, the interpolation of electroconductibility imparting agent and conducting film, obtain by making the polyamic acid that contains in above-mentioned polyamic acid solution or the gel-film carry out imidization, with
The sheet resistance value that records under impressed voltage 100V is 10 8～10 13In the scope of Ω/, and the volume resistance value is 10 8～10 14In the scope of Ω cm;
(2). a kind of manufacture method of semiconductive polyimide film, this method comprises: the organic solvent solution that will contain polyamic acid is as polyamic acid solution, again polyamic acid is partly solidified and/or partly dry and with the film that obtains during as gel-film,
To polyamic acid solution and/or gel-film, the electroconductibility of any at least a kind of operation of the formation of the interpolation of enforcement semi-conductivity mineral filler, the interpolation of electroconductibility imparting agent and conducting film is given operation; With,
After above-mentioned electroconductibility was given operation, the electroconductibility that makes the polyamic acid that contains in above-mentioned polyamic acid solution or the gel-film carry out imidization was given back imidization operation;
(3). a kind of semiconductive polyimide film wherein, contains the semi-conductivity mineral filler and is adding the sheet resistance value that records under the 100V voltage 10 in 15 weight %～50 weight % scopes 10Ω/～10 13In the scope of Ω/, and the volume resistance value is 10 10Ω cm～10 14In the scope of Ω cm;
(4). according to the semiconductive polyimide film described in (3), its tensile elongation is more than 40%;
(5). according to the semiconductive polyimide film described in (3), wherein, modulus in tension and anti tear transmission intensity be not for containing more than 1.1 times of polyimide film of above-mentioned semi-conductivity mineral filler;
(6). according to the semiconductive polyimide film described in (3), wherein, the semi-conductivity mineral filler be shaped as needle-like;
(7). according to the semiconductive polyimide film described in (3), wherein, the material of above-mentioned semi-conductivity mineral filler is a titanium oxide;
(8). according to the manufacture method of (2) described semiconductive polyimide film, comprising, in the semiconductive polyimide film that finally obtains, make the semi-conductivity mineral filler that contains in 15 weight %～50 weight % scopes, and in the homodisperse slurry of semi-conductivity mineral filler, be mixed with the polyamic acid solution that contains the semi-conductivity mineral filler by polymerization;
Make the film making solution curtain coating, the film forming on supporter that contain this polyamic acid solution;
Make logical superheated of this film or chemical method carry out the process of imidization.
(9). according to the manufacture method of the semiconductive polyimide film described in (2), comprising, in the semiconductive polyimide film that finally obtains, make the semi-conductivity mineral filler that contains in 15 weight %～50 weight % scopes, and polyamic acid solution and the homodisperse slurry of semi-conductivity mineral filler are mixed;
Make this mixed solution curtain coating, film forming on supporter;
Make logical superheated of this film or chemical method carry out the process of imidization;
(10). according to the manufacture method of the semiconductive polyimide film described in (2), comprising: the conducting film of gel-film at metal oxide formed with dipping in the coating fluid and/or coating;
Then, amido acid residual on the gel-film is carried out imidization, and, make this gel-film exsiccant process;
(11). according to the manufacture method of the semiconductive polyimide film described in (10), wherein, it is the solution that contains tin indium oxide that above-mentioned conducting film forms with coating fluid;
(12). according to the manufacture method of the semiconductive polyimide film described in (10), wherein, above-mentioned gel-film makes the semi-conductivity mineral filler that contains in the semiconductive polyimide film that finally obtains add the semi-conductivity mineral filler in 15 weight %～50 weight % scopes;
(13). according to the manufacture method of the semiconductive polyimide film described in (12), wherein, above-mentioned semi-conductivity mineral filler is a titanium oxide whisker;
(14). a kind of semiconductive polyimide film, this film are that the conducting film of gel-film at metal oxide formed with dipping in the coating fluid and/or coating; Then, amido acid residual on the gel-film is carried out imidization, and, make by making this gel-film drying;
(15). according to the semiconductive polyimide film described in (14), wherein, the sheet resistance value that records under impressed voltage 100V is 10 8Ω/～10 12In the scope of Ω/, the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm;
(16). according to the manufacture method of the semiconductive polyimide film described in (2), comprising: by being mixed, polyamic acid solution and electroconductibility imparting agent solution is mixed with film making solution;
This film making solution is delayed at the supporter upper reaches carried out imidization, and carry out the exsiccant process.
(17). according to the manufacture method of the semiconductive polyimide film described in (16), wherein, above-mentioned electroconductibility imparting agent is metal oxide and/or its precursor;
(18). according to the manufacture method of the semiconductive polyimide film described in (17), wherein, above-mentioned metal oxide is a tin indium oxide;
(19). according to the manufacture method of the semiconductive polyimide film described in (16), wherein, above-mentioned film making solution is to make the semi-conductivity mineral filler that contains in the semiconductive polyimide film that finally obtains add the semi-conductivity mineral filler in 15 weight %～50 weight % scopes;
(20). according to the manufacture method of the semiconductive polyimide film described in (19), wherein, above-mentioned semi-conductivity mineral filler is a titanium oxide whisker;
(21). a kind of semiconductive polyimide film, wherein, by polyamic acid solution and electroconductibility imparting agent solution or dispersion liquid are mixed, be mixed with film making solution, this film making solution is delayed at the supporter upper reaches carried out imidization, and carry out drying and make;
(22). according to the semiconductive polyimide film described in (21), in addition, the sheet resistance value that records under impressed voltage 100V is 10 8Ω/～10 12In the scope of Ω/, the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm.
Other purposes of the present invention, feature and advantage can clearly be understood from following explanation.In addition, interests of the present invention are understood by the following explanation of reference accompanying drawing.
Embodiment
Below 1 embodiment of the present invention is described in detail as follows.But the present invention is not limited to by it.
The semiconductive polyimide film that the present invention relates to can be given the manufacture method of the imidization operation after operation and electroconductibility are given and obtains by containing electroconductibility, and is to become the sheet resistance value measured 10 under impressed voltage 100V 8Ω/～10 13In the scope of Ω/, and the volume resistance value is 10 8Ω cm～10 14Formation in the scope of Ω cm.
In addition, the semiconductive polyimide film manufacture method that the present invention relates to is to contain above-mentioned electroconductibility to give the method that operation and electroconductibility are given back imidization operation.
Above-mentioned electroconductibility is given operation, be (following for ease of explanation to the organic solvent solution that contains polyamic acid, be called polyamic acid solution) and/or gel-film, interpolation, the interpolation of electroconductibility imparting agent and the conducting film of implementing the semi-conductivity mineral filler form at least a kind operation.In addition, above-mentioned electroconductibility is given back imidization operation, is after above-mentioned electroconductibility is given operation, the polyamic acid that contains in above-mentioned polyamic acid solution or the gel-film is carried out the operation of imidization.
Below, along the flow process of semiconductive polyimide film manufacture method, describe semiconductive polyimide film of the present invention and manufacture method thereof in detail.
Give operation in above-mentioned electroconductibility,, give electroconductibility by various methodologies to polyamic acid solution and/or gel-film.Therefore, also contain above-mentioned polyamic acid solution preparation process and/or gel-film molding procedure in the manufacture method that the present invention relates to.
＜polyamic acid solution preparation process 〉
The semiconductive polyimide film that the present invention relates to is given operation and electroconductibility except that above-mentioned electroconductibility and is given the imidization operation of back, is to adopt original known method to make basically.Therefore, the polyimide that the present invention uses is by making the polyamic acid as precursor, this polyamic acid imidization being obtained.Therefore, in the present invention, be preferred when containing the polyamic acid solution preparation process.
The polyamic acid that the present invention is used, usually, it is at least a kind and at least a kind of diamines with the aromatic acid dianhydride, be dissolved in the organic solvent with equimolar amount in fact, the polyamic acid solution that obtains under the temperature condition of control, is finished by being stirred to above-mentioned acid dianhydride and diamines that polymerization makes.In the present invention, can adopt several polymerization processs to obtain polyamic acid solution, but can enumerate as an example:
1) with the aromatic acid dianhydride with solid state, paste-like, solution shape or their combination, add dissolving to or disperse method in the organic solvent of diamines;
2) with diamines with solid state, paste-like, solution shape or their combination, add dissolving to or disperse method in the organic solvent of aromatic acid dianhydride;
3) in order to control monomeric arrangement in the polyamic acid molecule, add each monomer, finally make the method for equimolar in fact aromatic acid dianhydride and diamine reactant with multistage; Deng.
In addition, also can mix the polyamic acid solution more than 2 kinds that other polymerization process obtains the back uses.The concentration of these polyamic acid solutions and viscosity, can consider suitably to regulate according to its purposes, process synthesis, but can obtain usually having in 5 weight %～35 weight % scopes, preferably reach concentration in 10 weight %～30 weight % scopes, under 23 ℃ mensuration temperature, in 50 pools～10000 pool scopes, the solution of viscosity in preferred 100 pools～5000 pool scopes.Suitable molecular weight when most occasions can obtain the concentration of above-mentioned scope and soltion viscosity.
Above-mentioned polyamic acid solution obtains with the concentration of 10 weight %～30 weight % usually.When in this concentration range, can realize molecular weight and soltion viscosity that imidization is suitable.Certainly, the preparation process of polyamic acid solution of the present invention is not limited to this, adopts the polyamic acid composition that the additive method contain polyamic acid also can the obtain solution shape.
There is no particular limitation for operable aromatic acid dianhydride during above-mentioned polyamic acid was made, but concrete can enumerating, for example equal benzene tertacarbonic acid's dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 2, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2-, 3,4,9, the 10-AEp tetracarboxylic dianhydride, two (3,4-dicarboxyl phenyl) propane dianhydride, 1,1-two (2,3-dicarboxyl phenyl) ethane dianhydride, 1, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1-, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) ethane dianhydride, oxo two phthalandione dianhydrides, two (3,4-dicarboxyl phenyl) sulfonic acid dianhydride, p-phenylene two (trimellitic acid monoesters acid anhydrides), ethylenebis (trimellitic acid monoesters acid anhydrides), dihydroxyphenyl propane two (trimellitic acid monoesters acid anhydrides) and their analogue etc. can preferably use.These aromatic acid dianhydrides both can use separately, and also ratio is mixed as mixture and used arbitrarily.
In above-mentioned aromatic acid dianhydride, as particularly preferred compound, can enumerate pyromellitic acid anhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, p-phenylene two (trimellitic acid monoesters acid anhydrides).These compounds and above-mentioned same also can use separately or as mixture.
There is no particular limitation for operable diamines during above-mentioned polyamic acid was made, but concrete can enumerate, for example 4,4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenyl-methane, p-diaminodiphenyl, 3,3 '-dichlorobenzidine, 4,4 '-diamino-diphenyl thioether, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 4,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 1, the 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, 1,4-diaminobenzene (p-phenylenediamine), 1, the 3-diaminobenzene, 1,2-diaminobenzene and their analogue etc. can preferably use.These diamines can use separately, or are mixed as mixture with ratio arbitrarily and to use.
In above-mentioned diamines, as particularly preferred compound, can enumerate 4,4 '-diamino-diphenyl ether and p-phenylenediamine.These compounds can use separately, these compounds also can mol ratio 90: 10～10: 90 scope, preferred 85: 15～20: 80 scope, more preferably use 80: 20～30: 70 in addition mixed mixture also be preferred the use.
Spendable organic solvent when above-mentioned polyamic acid is synthetic is not particularly limited, and for example, concrete can preferably use N, amide solvents such as dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-.These organic solvents both can use separately, or were mixed as mixture with arbitrary proportion and to use.
In the above-mentioned organic solvent, N, dinethylformamide or N,N-dimethylacetamide are preferred the uses.These solvents and above-mentioned same also can use separately or as mixture.
The preparation condition of polyamic acid solution preparation process of the present invention promptly, is not particularly limited creating conditions of polyamic acid solution.Concrete is, the agitation condition of the ratio of components of the above-mentioned monomer solution of preparing for the polyamic acid polymerization, temperature condition, monomeric interpolation order or the monomer solution controlled for the polyamic acid polymerization etc., get final product so long as can synthesize the condition of desirable polyamic acid solution, can suitably adopt original known condition.
＜gel-film molding procedure 〉
In the present invention, to above-mentioned polyamic acid solution or gel-film, can implement electroconductibility and give operation.Therefore, can also contain the gel-film molding procedure that makes above-mentioned gel-film moulding among the present invention.
At the gel-film of above-mentioned gel-film molding procedure moulding, refer to the partly solidified and/or dry film that is constituted of part of polyamic acid, can adopt original known method manufacturing.Concrete is that for example the polyamic acid solution that obtains at above-mentioned polyamic acid preparation process, curtain coating, coating on supporting mass obtain its curing by chemistry or heating method.
Reduce for fear of rerum naturas such as the toughness of the semiconductive polyimide film that finally obtains and breaking tenacitys, or in order to avoid the reduction of production efficiency easily, it is preferred adopting chemosetting.Certainly, should be according to the purposes of semiconductive polyimide film and gel-film or kind etc., it is suitable adopting thermal curing method sometimes, this is self-evident.
Above-mentioned curing, the imidization of concrete finger polyamic acid in this imidization, can adopt any of method of heat curing system, chemicure method or these methods and usefulness all can.Heat curing system is equivalent to above-mentioned thermal curing method, and the chemicure method is equivalent to above-mentioned chemosetting method.
Above-mentioned heat curing system is not use dehydration ring closure agent etc. and the method for only carrying out imidization reaction with heating.The temperature of above-mentioned heating and other condition can suitably adopt original known condition, and there is no particular limitation.
Above-mentioned chemicure method is to make chemical converting agent and preferred catalyst action in polyamic acid solution, carries out the method for imidization.
Concrete kind to above-mentioned chemical converting agent is not particularly limited, for example, aliphatic anhydride, aromatic anhydride, N, N '-dialkyl group carbodiimide, lower aliphatic halogenide, halogenated lower aliphatics halogenide, halogenated lower fatty acid anhydride, aryl phosphoric acids dihalide, thionylhalides etc. are preferred.These chemical converting agents both can use separately, can be used as two or more mixtures again and used.
In above-mentioned chemical converting agent, can enumerate aliphatic anhydride such as acetic anhydride, propionic anhydride, butyryl oxide as particularly preferred compound.These compounds also with above-mentioned same, both can use separately or as two or more mixtures.
There is no particular limitation for the consumption of above-mentioned chemical converting agent, but, to 1 mole of the amido acid in the polyamic acid, in 0.5 molar equivalent～5.0 molar equivalent scopes, get final product, preferably in 0.8 equivalent～4.0 molar equivalent scopes, more preferably in 1.0 equivalents～3.0 molar equivalent scopes, use.
When the consumption of chemical converting agent was lower than above-mentioned scope, imidization had slack-off tendency, and production efficiency has the danger of reduction.In addition, when being higher than above-mentioned scope, the mechanical characteristics of resulting polyimide film worsens, and the excessive velocities of imidization has the danger that is difficult to curtain coating on base material.
In order effectively to carry out imidization, above-mentioned catalyzer can also be used simultaneously with chemical converting agent.The concrete kind of this catalyzer is not particularly limited, and still, for example can adopt aliphatic tertiary amine, aromatic nitrile base, hetero ring type tertiary amine etc. as catalyzer.Wherein, the compound of selecting from the hetero ring type tertiary amine is particularly preferred.It is preferred can adopting quinoline, isoquinoline 99.9, β-picoline, pyridine etc. more specifically.
Above-mentioned catalyst consumption is not particularly limited, to 1 mole of the amido acid in the polyamic acid, as long as in the scope of 0.1 equivalent～2 molar equivalents, preferably in the scope of 0.2 equivalent～1.5 molar equivalents, more preferably the use of the ratio of 0.3 equivalent～1.0 molar equivalents is preferred.
When above-mentioned catalyst consumption is lower than above-mentioned scope when very few (), chemical imidization (curing) has and is difficult to the tendency of carrying out.In addition, when being higher than above-mentioned scope (too much time), chemical imidization (curings) has the tendency that accelerates, and the curtain coating on supporter has the danger that becomes difficult.
Above-mentioned chemicure method and heat curing system both can use separately also and can and use.In addition, no matter be separately and usefulness, the reaction conditions that imidization relates to is that the selection etc. of thickness, chemicure method and/or the heat curing system of kind, gel-film or polyimide film according to polyamic acid is changed and is not particularly limited.
Above-mentioned chemicure method and heat curing system, can gel-film electroconductibility is given give electroconductibility in the operation after, or give in the imidization operation of back in electroconductibility and to implement.Give in the imidization operation of back in electroconductibility, finish imidization, make semiconductive polyimide film, but, in above-mentioned gel-film molding procedure, be necessary, suppress imidization and reach degree, to rest on from the intermediate stage of polyamic acid to polyimide curing with self-supporting.
Here, above-mentioned gel-film contains the volatile amount V (% of unit) that calculates from following formula (1) and is in that the person is preferred in the specialized range.Also have, the A in the following formula (1) is meant the weight of gel-film, and B refers to gel-film in the weight of 450 ℃ of heating after 20 minutes, and C refers to the content (weight %) of semi-conductivity mineral filler contained in the gel-film.To the semi-conductivity mineral filler, give operation in following electroconductibility and described in detail.In addition, the weight unit among the above-mentioned AB is as long as be the unit (for example, A is g (gram), and B also is g (gram)) of homogeneous unit and being not particularly limited respectively.
V＝(A-B)×100/{B×(100-C)} (1)
Above-mentioned volatile component content V gets final product in 5%～500% scope, in preferred 5%～100% scope, more preferably in 10%～80% scope, most preferably in 30%～60% scope.In above-mentioned scope, the quality of resulting semiconductive polyimide film is preferred as the volatile component content V of gel-film, but if beyond above-mentioned scope the time, is difficult to present the effect of regulation.
In addition, in resulting semiconductive polyimide film, for the more reliable effect that presents regulation, the imidization rate of control gel-film is preferred.
The mensuration of this imidization rate I (unit %) in not containing the gel-film (i.e. gel-film by polyamic acid solution moulding) of semi-conductivity mineral filler and conducting film formation with coating fluid, adopts infrared rays absorptiometric analysis method, calculates from following formula (2).Also have, form about conducting film and use coating fluid, same with the semi-conductivity mineral filler, give operation in following electroconductibility and describe in detail.In addition, the D in following formula (2) is meant that gel-film is at 1370cm -1The absorption peak height, E is meant that gel-film is at 1500cm -1The absorption peak height, F is meant that polyimide film is at 1370cm -1The absorption peak height, G is meant that polyimide film is at 1500cm -1The absorption peak height.
I＝(D/E)×100/(F/G) (2)
Above-mentioned imidization rate I is not particularly limited, and as preferred range be: lower limit is getting final product more than 50%, and is preferred more than 80%, more preferably more than 85%, most preferably more than 90%.Certainly, the upper limit is 100%.When the imidization rate I of gel-film was in the above-mentioned scope, resulting polyimide film was superior in quality, and when beyond the above-mentioned scope, was difficult to present the effect of regulation.
In the present embodiment, can be intact from the polyamic acid solution that above-mentioned polyamic acid solution preparation process obtains as film making solution, or polyamic acid solution implemented the interpolation of following semi-conductivity mineral filler and the interpolation of electroconductibility imparting agent makes film making solution later on.Then, be moulded this film making solution membranaceous at tabular supporter (base material) direct casting.Above-mentioned supporter on, the temperature range of regulation in pass through heating, make polyamic acid partly solidified and/or dry thereafter.Then, peel off, make gel-film from above-mentioned supporter.
The kind of above-mentioned supporter is not particularly limited, and for example, can enumerate sheet glass, aluminium foil, ring-type Stainless Steel Band, stainless steel drum etc.Size to these supporters also is not particularly limited.Condition during in addition, to casting film making solution on above-mentioned supporter also is not particularly limited.
Heating temperature about polyamic acid when partly solidified and/or dry is wished in 80 ℃～200 ℃ scope, preferably in 100 ℃～180 ℃ scope.When beyond this scope, production efficiency descends, or easily produces defective such as foaming.
＜electroconductibility is given operation 〉
As mentioned above, in the present invention, give operation to above-mentioned polyamic acid solution or gel-film enforcement electroconductibility.This electroconductibility is given operation, and concrete is implements interpolation, and at least 1 operation of the formation of conducting film of interpolation, the electroconductibility imparting agent of semi-conductivity mineral filler to polyamic acid solution and/or gel-film.As follows about specifying of giving of above-mentioned each electroconductibility.
The interpolation of＜semi-conductivity mineral filler 〉
The above-mentioned semi-conductivity mineral filler of using among so-called the present invention (following for ease of explanation, as only to be called mineral filler) is meant that mineral filler with drying regime is at 100kg/cm 2The formed body of pressure lower compression moulding, its volume specific resistance (powder resistance) is 10 5～10 9The filler of Ω cm.
The originally mineral filler of Shi Yonging is electroconductive stuffing or the particle that coats with carbon and graphite etc.Therefore, resistance value is low, also reduces easily even add resistance value on a small quantity.In contrast, used semi-conductivity mineral filler among the present invention owing to have above-mentioned formation, shows resistance value in the semi-conductivity zone, in order to reduce resistance value, must add amount to a certain degree.Therefore, by changing addition, can carry out the fine adjustments of resistance value.The result is, the sheet resistance value of resulting polyimide film not only, and, suitable control volume resistance value, however these resistance value deviations are little, and are also little to the dependency of voltage.
Its material is not particularly limited, preferably can adopts, for example titanium oxide, zinc oxide, ferric oxide, lime carbonate, ironic hydroxide, stannic oxide etc.Wherein, from the viewpoint of the thermotolerance of resulting semiconductive polyimide film, resistance control etc., it is most preferred adopting titanium oxide.
Shape to above-mentioned mineral filler is not particularly limited, and shape such as spherical, stratiform, needle-like, powder shape all can.The mineral filler of these different shapes both can be used separately, also can be more than 2 kinds in addition the using as mixture after the mixing of shape.Wherein, adopt acicular mineral filler, or the mixture of the mineral filler of needle inorganic filler and other shapes is preferred.Therefore, acicular during when adopting at least as mineral filler, consider it is preferred from the viewpoint of the mechanical characteristics of resulting semiconductive polyimide film.
Therefore, the preferred especially mineral filler of using among the present invention, can to enumerate material be titanium oxide, it is acicular to be shaped as, i.e. titanium oxide whisker.
As above-mentioned needle inorganic filler shape more specifically, be not particularly limited, for example, as long as the minor axis diameter is in 0.01 μ m～1 mu m range, preferably in the scope of 0.05 μ m～0.75 μ m, more preferably in 0.1 μ m～0.5 mu m range.In addition, major diameter gets final product at 1 μ m～20 mu m ranges, preferably in the scope of 1.5 μ m～15 μ m, more preferably in 2 μ m～10 mu m ranges.
When the minor axis diameter of mineral filler and major diameter are not in above-mentioned scope, the balance difficulty of the resistance value of resulting semiconductive polyimide film and physical strength.
During other shape mineral fillers beyond adopting above-mentioned needle-like, its median size is that the scope of 0.01 μ m～20 μ m gets final product, the scope of preferred 0.01 μ m～15 μ m, the more preferably scope of 0.01 μ m～10 μ m.
When the particle diameter of mineral filler is lower than above-mentioned scope when too small (), the mechanical property of resulting semiconductive polyimide film has the tendency of decline.In addition, when being higher than above-mentioned scope when excessive (), the resistance value of resulting semiconductive polyimide film has unmanageable tendency.
The addition of above-mentioned mineral filler, not being particularly limited, still, is to get final product in the scope of 15 weight %～50 weight % with respect to the semiconductive polyimide film gross weight, in the scope of preferred 15 weight %～40 weight %, more preferably in the scope of 20 weight %～35 weight %.
In addition, in the present invention, give operation,,, but also can and use with other electroconductibility adding methods so the interpolation of mineral filler is optional owing to can adopt other electroconductibility adding methods in electroconductibility.At this moment, preferred mineral filler addition has some different with above-mentioned addition sometimes.
For example, in the interpolation and the time spent of mineral filler interpolation and electroconductibility imparting agent, also can (certainly, how also harmless) even the mineral filler addition is few.Therefore, with the interpolation and time spent of electroconductibility imparting agent, as long as the lower limit of the addition of mineral filler can be brought into play the effect of giving sufficient conductivity about 10 weight %.
When the addition of mineral filler was less than above-mentioned scope, the electroconductibility of resulting semiconductive polyimide film was difficult to improvement.In addition, when being higher than above-mentioned scope, the volume resistance value and the sheet resistance value of resulting semiconductive polyimide film are nearly approximate saturated, and the extensibility of this semiconductive polyimide film has the tendency of decline.
The concrete grammar of the interpolation of above-mentioned semi-conductivity mineral filler is not particularly limited.At first, when the object that adds mineral filler is polyamic acid solution, be not particularly limited at dispersive concrete grammar in polyamic acid solution, no matter its whether with other electroconductibility adding method and usefulness, any method can be used.
Concrete can enumerate (i) with having disperseed the slurry of mineral filler to make polyamic acid polymeric method as polymer solvent; (ii) add the slurry of mineral filler or mineral filler midway, the method for the polyamic acid solution of preparation fillers dispersed in polymerization; (iii) will on base material, carry out blended method etc. to the slurry of polyamic acid solution and mineral filler before the curtain coating.Also have, when adopting the method for (i), the interpolation of mineral filler is to implement simultaneously with the polyamic acid solution preparation process, when the polyamic acid solution preparation process stops, can obtain the polyamic acid solution of fillers dispersed.
In the present embodiment, when after the electroconductibility of back segment is given, adopting above-mentioned heat curing system in the imidization operation, can use as film making solution by intact polyamic acid solution above-mentioned fillers dispersed.In addition, when adopting above-mentioned chemicure method, toward the polyamic acid solution of above-mentioned fillers dispersed in, add chemical converting agent, and preferably the interpolation solidifying agent that contains catalyzer also can as film making solution.Make mineral filler dispersive slurry in this solidifying agent,, also can as film making solution by in polyamic acid solution, adding this solidifying agent-mineral filler whisker.
In addition, when the object that adds mineral filler was gel-film, the concrete grammar that adds toward gel-film was not particularly limited.For example, make the fillers dispersed liquid that disperses mineral filler,, also added mineral filler in the gel-film in the past by this fillers dispersed liquid is coated on the gel-film.
The interpolation of＜electroconductibility imparting agent 〉
The electroconductibility imparting agent that the present invention is used so long as be cured, give getting final product of electroconductibility to the polyimide film that finally obtains, is not particularly limited it, for example, can enumerate various metal oxides or its precursor.As this metal oxide, for example concrete, can enumerate adulterated al or boron zinc oxide, stannic oxide, titanium oxide, Indium sesquioxide, zinc-indium oxide, add antimony stannic oxide, add the Indium sesquioxide (tin indium oxide) of tin etc.
Above-mentioned metal oxide both can use separately, also can adopt more than 2 kinds.In addition, during as the electroconductibility imparting agent, when sneaking into polyamic acid, also can contain its precursor with above-mentioned metal oxide.As above-mentioned precursor, if when being mixed with solution, become above-mentioned metal oxide can and the end is particularly limited, when metal oxide is tin indium oxide, for example, can enumerate indium formate and formic acid tin (II).
Give operation in electroconductibility of the present invention, the above-mentioned electroconductibility imparting agent that is in solution state is sneaked into to use behind the polyamic acid solution also can.
By adopting this electroconductibility imparting agent solution, owing to can mix electroconductibility imparting agent that is in molecular level and polyamic acid, so, then can easily and accurately the volume resistance value and the sheet resistance value of resulting semiconductive polyimide film be controlled by in a small amount of interpolation in semi-conductivity zone.And the resistance value deviation in the voltage-dependent of above-mentioned each resistance value and the polyimide face also can diminish.
Particularly, in the present invention as the solution that contains above-mentioned precursor, can be using as electroconductibility imparting agent solution for solutions employed before this (conducting film forms and the uses coating fluid) former state that forms the metal conductive oxide film.That is, in the interpolation of electroconductibility imparting agent, the conducting film formation coating fluid containing above-mentioned metal oxide as electroconductibility imparting agent solution, also can be blended in the polyamic acid organic solvent solution.
By above-mentioned conducting film is formed with coating fluid as electroconductibility imparting agent solution, not only can obtain the effect that the resistance value of the semiconductive polyimide film of gained descends, and also reduced the voltage-dependent of resistance value, and, can also obtain the effect that the resistance value deviation in the face of semiconductive polyimide film reduces.
Form with in the coating fluid at above-mentioned original known conducting film, the solution (for ease of explanation, being called ITO precursor coating fluid) that contains the tin indium oxide precursor is preferred.This ITO precursor coating fluid, obtains easily and from low this point of cost, also is preferred widespread use usually.Particularly, for example, can adopt disclosed indium tin oxides film such as above-mentioned " spy opens flat 11-279437 communique " and above-mentioned " spy opens the 2000-207959 communique " to form and use coating fluid.
The addition of above-mentioned electroconductibility imparting agent solution is not particularly limited, and can suitably set according to the kind of electroconductibility imparting agent to get final product.For example, the occasion of above-mentioned ITO precursor coating fluid, its addition converts as tin indium oxide weight, with respect to the weight of polyimide is to get final product in the scope of 1 weight part～20 weight parts, in the scope of preferred 1.5 weight parts～15 weight parts, more preferably in the scope of 2 weight parts～10 weight parts.
When above-mentioned addition was very few, the electroconductibility of resulting semiconductive polyimide film was improved effect and is difficult to occur, and has served as for a long time, and the physical strength of polyimide film has the tendency of decline.
In addition, in the present invention, as conducting film formation coating fluid, can adopt Japan openly to specially permit the precursor solution of disclosed metal oxide of communique " spy opens flat 7-331450 communique " (open day December 19 nineteen ninety-five), " spy opens flat 8-227614 communique " (open day on September 3rd, 1996), " spy opens flat 8-295513 communique " (open day on November 12nd, 1996), " spy opens flat 9-286936 communique " (open day on November 4th, 1997), as the electroconductibility imparting agent solution among the present invention.
The operation of above-mentioned electroconductibility imparting agent solution being sneaked into (containing electroconductibility formation coating fluid) polyamic acid solution is not particularly limited, and is same with the interpolation of above-mentioned mineral filler, can implement in any stage yet.For example, can enumerate (I) the method for electroconductibility imparting agent solution as the polyamic acid polymer solvent; (II) in the polyamic acid polymerization method of mixed conductivity imparting agent solution midway; (III) will be before curtain coating on the supporter electroconductibility imparting agent solution and polyamic acid solution blended method etc. in addition.Wherein, consider that from the storage stability of polyamic acid solution it is preferred (III) will carrying out the blended method before curtain coating on the supporter.
Therefore, when the electroconductibility that adopts back segment is given above-mentioned heat curing system in the imidization operation of back, contain the polyamic acid solution of above-mentioned electroconductibility imparting agent solution, but former state is used as film making solution.This also with and same with the occasion of the interpolation of the interpolation of electroconductibility imparting agent and mineral filler.That is, but the polyamic acid solution that contains mineral filler and electroconductibility imparting agent solution also former state use as film making solution.
In addition, when the electroconductibility that adopts back segment is given above-mentioned heat curing system in the imidization operation of back, in the polyamic acid solution that contains above-mentioned electroconductibility imparting agent solution, add chemical converting agent and the preferred solidifying agent that contains catalyzer that adds, also can as film making solution, the perhaps mixed solution of preparation mixed conductivity imparting agent solution in this solidifying agent is added into this solidifying agent-electroconductibility imparting agent solution and makes film making solution in the polyamic acid solution and also can.
Same, interpolation and the interpolation of mineral filler and the occasion of usefulness at the electroconductibility imparting agent, in the polyamic acid solution that contains mineral filler and electroconductibility imparting agent solution, add chemical converting agent and the preferred solidifying agent that contains catalyzer that adds, or, be added in the polyamic acid solution and also can obtain film making solution earlier after solidifying agent and the mixing of electroconductibility imparting agent solution.
The formation of＜conducting film 〉
The conducting film that forms among the present invention gets final product so long as contain the metal conductive oxide film of the metal oxide of enumerating in the above-mentioned electroconductibility imparting agent, and is not particularly limited.This conducting film is by the dissolving of above-mentioned metal oxide or its precursor or be dispersed in the conducting film that obtains in the organic solvent and form with coating fluid and form.
Above-mentioned conducting film forms the concentration with coating fluid, is not particularly limited, but as long as in 0.01 weight %～15 weight % scopes, preferably in 0.05 weight %～10 weight % scopes, more preferably in 0.1 weight %～5 weight % scopes.
Cross when hanging down when above-mentioned conducting film forms with the concentration of coating fluid, the electroconductibility of resulting semiconductive polyimide film is improved effect and is difficult to present.In addition, when above-mentioned conducting film formed the excessive concentration of using coating fluid, the physical strength of resulting semiconductive polyimide film had the tendency of reduction.
In addition, in semiconductive polyimide film, consider from the viewpoint that the voltage-dependent of its resistance value diminishes, the concentration that above-mentioned conducting film forms with coating fluid is that 0.1 weight %～15 weight % scopes are preferred, 0.25 weight %～10 weight % scopes are preferred, 0.5 weight %～5 weight % scopes are more preferably.
When above-mentioned conducting film formed density loss 0.1 weight % with coating fluid, in resulting semiconductive polyimide film, particularly the effect that diminishes of the voltage-dependent of volume resistance value reduced.In addition, when above-mentioned conducting film formed with the excessive concentration of coating fluid, the physical strength of resulting semiconductive polyimide film had the tendency of reduction.
The solvent that above-mentioned conducting film forms with coating fluid is not particularly limited, and can adopt originally known severally, but preferably can adopt amide solvent, that is, and and N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-etc.Wherein, N, dinethylformamide or N,N-dimethylacetamide can be separately or use with the mixture of arbitrary proportion, are preferred.
Above-mentioned conducting film forms and use coating fluid, also illustrates in the interpolation of above-mentioned electroconductibility imparting agent, can adopt originally known those, and be not particularly limited.Concrete can adopt, and for example, it is preferred that disclosed indium tin oxides film such as above-mentioned " spy opens flat 11-279437 communique " and above-mentioned " spy opens the 2000-207959 communique " forms with coating fluid etc.
Adopt above-mentioned conducting film to form and handle above-mentioned gel-film with coating fluid, promptly, on gel-film, form conducting film, whereby, give electroconductibility to the polyimide film that finally obtains, and can make semiconductive polyimide film, simultaneously, the voltage-dependent of the resistance value of the semiconductive polyimide film that obtains as mentioned above, also can diminish.Also having, become the gel-film that conducting film forms object, both can be the gel-film that has added mineral filler, also can be the gel-film that does not add mineral filler.
Form the method for handling with coating fluid as above-mentioned gel-film with conducting film, the method for conducting film gets final product and work is special limits so long as form on gel-film, can adopt previous known method.Particularly, can preferably adopt on gel-film the coating conducting film to form coating method, or gel-film is immersed in conducting film forms with the pickling process in the coating fluid with coating fluid.
Above-mentioned coating method can adopt previous known the whole bag of tricks and not be particularly limited, and for example, can adopt wheel to change coating methods such as gravure coating method, spraying method, scraper coating method.Wherein, from glue spread control and inhomogeneity viewpoint, it is preferred especially the use that wheel changes the gravure coating method.
Form the glue spread of using coating fluid as above-mentioned conducting film, be not particularly limited, but 1g/m 2More than be preferred, 5g/m 2More than be preferred.When glue spread is lower than this scope, the electrology characteristic of resulting semiconductive polyimide film is improved effect descend.
Above-mentioned pickling process is not particularly limited yet, can adopts general dip coated method.Particularly, be gel-film to be immersed in continous way or discontinuous fill conducting film formation with in the groove of coating fluid.Dipping time is not particularly limited, but common be preferred more than 1 second.When dipping time was more too short than it, the effect of improving of volume resistance value had the tendency that diminishes.In addition, for the resistance value of resulting semiconductive polyimide film is transferred to desirable value, the operation of pickling process also can repeat more than 2 times.
In above-mentioned conducting film formed, coating method and pickling process both can have been distinguished enforcement separately, also combinable enforcement.Particularly, in order to control or improve the resistance characteristic and the electrology characteristic of resulting semiconductive polyimide film, coating method and pickling process and with being preferred.
In addition, in the present embodiment, to gel-film, form with after the coating fluid processing (dipping and/or coating) with conducting film, the schedule of operation that increases the residue drop of removing gel film surface is preferred.Whereby, on gel film surface, can form immaculate conducting film, so, the semiconductive polyimide film of outward appearance grace can be obtained.
The method of removing to above-mentioned drop is not particularly limited, and it is preferred adopting previous known the whole bag of tricks.Concrete can enumerate, and for example uses the methods such as mangle, air knife, scraper, wiping, absorption of extrusion roll.Wherein, remove viewpoints such as property, operation from the outward appearance of film, liquid and consider that it is preferred adopting the mangle method of extrusion roll.
＜electroconductibility is given the change of operation 〉
As mentioned above, for electroconductibility is given operation, both can adopt the adding method of above-mentioned each electroconductibility individually also capable of being combinedly, below its change specified.
Implement electroconductibility and give the moment of operation, both can be at the leading portion of gel-film molding procedure, promptly, in the time of with the polyamic acid solution preparation process or behind the polyamic acid solution preparation process, also can be after the gel-film molding procedure, in addition, also can be respectively after above-mentioned various operations.With polyamic acid solution preparation process occasion simultaneously, be when preparing with polyamic acid solution, implement the interpolation of mineral filler and/or the interpolation of electroconductibility imparting agent, after the polyamic acid solution preparation process, polyamic acid solution is implemented the interpolation of mineral filler and/or the interpolation of electroconductibility imparting agent, after the gel-film molding procedure, implement the interpolation (for example, the coating of fillers dispersed liquid) of mineral filler and/or the formation of conducting film.
Here, as mentioned above, when the formation of the interpolation of electroconductibility imparting agent and conducting film, can adopt same conducting film to form and use coating fluid, so, give the concrete change of electroconductibility, be summarized in following (A)～(C).
(A) only in polyamic acid solution preparation or thereafter
To polyamic acid solution (in the preparation, preparation back), interpolation, (A-2) conducting film that only carries out (A-1) mineral filler forms that mineral filler and conducting film form interpolation with coating fluid with the interpolation of coating fluid or (A-3).
(B) only after the gel-film molding procedure
To gel-film, the interpolation (coating of fillers dispersed liquid), (B-2) conducting film of only carrying out (B-1) mineral filler forms that fillers dispersed liquid and conducting film formation are coated with coating fluid with the coating of coating fluid or (B-3).
(C) after polyimide acid solution preparation process and gel-film molding procedure two-step
(C-1) polyamic acid solution is only carried out the occasion of the interpolation of mineral filler
To polyamic acid solution, after carrying out the interpolation of mineral filler, to the gel-film that obtains, the interpolation (coating of fillers dispersed liquid), (C-1-2) conducting film of carrying out (C-1-1) mineral filler forms that fillers dispersed liquid and conducting film form coating with coating fluid with the coating of coating fluid or (C-1-3).
(C-2) polyamic acid solution is only carried out the occasion that conducting film forms the interpolation of using coating fluid
To polyamic acid solution, carrying out conducting film forms with after the interpolation of coating fluid, to the gel-film that obtains, the interpolation (coating of fillers dispersed liquid), (C-2-2) conducting film of carrying out (C-2-1) mineral filler forms that fillers dispersed liquid and conducting film form coating with coating fluid with the coating of coating fluid or (C-2-3).
(C-3) polyamic acid solution is carried out mineral filler and conducting film and form occasion with the interpolation of coating fluid
To polyamic acid solution, carrying out mineral filler and conducting film forms with after the interpolation of coating fluid, to the gel-film that obtains, the interpolation (coating of fillers dispersed liquid), (C-3-2) conducting film of carrying out (C-3-1) mineral filler forms that fillers dispersed liquid and conducting film form coating with coating fluid with the coating of coating fluid or (C-3-3).
In the present invention, the concrete grammar that electroconductibility is given is not particularly limited, and for example, gives in the operation in electroconductibility, both can adopt any method of above-mentioned (A)～(C), can adopt the combination of several different methods yet.
＜electroconductibility is given back imidization operation 〉
As what illustrate in above-mentioned gel-film molding procedure, be moulded above-mentioned film making solution membranaceous at the supporter direct casting, in 80 ℃～200 ℃ temperature range, heating on this supporter,, obtaining partly solidified and/or the exsiccant gel-film again by from supporter, it being peeled off.This gel-film was in from the intermediate stage of polyamic acid to polyimide curing.
And, illustrate in the operation as giving in above-mentioned electroconductibility, adopt interpolation, and any at least operation of the formation of conducting film of interpolation, the electroconductibility imparting agent of mineral filler, give electroconductibility to the gel-film before the moulding or after the moulding.This gel-film constantly is the gel-film that contains (a) mineral filler and/or electroconductibility imparting agent, perhaps (b) is that the gel-film that forms conducting film is gone up on the surface, perhaps (c) contains mineral filler and/or electroconductibility imparting agent and surface to go up the gel-film that forms conducting film and constitute, the incomplete imidization (curing) of polyamic acid.
Here, give in the imidization operation of back, make the gel-film of having given above-mentioned (a)～(c) electroconductibility carry out imidization in electroconductibility.This moment imidization concrete grammar, it is preferred can adopting the heat curing system or the chemicure method that illustrate in the above-mentioned gel-film molding procedure.
Here, adopt electroconductibility to give back imidization operation, the contraction that causes for fear of imidization, the end of preferred above-mentioned gel-film is fixed, therefore, and after the end is fixing, the desiccant gel film, remove anhydrate, residual solvent, residual transforming agent or catalyzer etc., by the complete imidization of residual amido acid, the semiconductive polyimide film that can obtain the present invention relates to.
Here, the heat treated after electroconductibility is given in the imidization operation, it is preferred finally implementing with the temperature and time of following scope.Temperature range is in 400 ℃～580 ℃ scope, in preferred 450 ℃～550 ℃ scope.Time is in 1 second～500 seconds scope, in preferred 15 seconds～400 seconds scope.
In heat treated, at least, when temperature is longer than the above-mentioned scope of above-mentioned scope height or time ratio, cause the thermal degradation when of gel-film, the mechanical characteristics of resulting semiconductive polyimide film has the danger that reduces takes place.Otherwise, temperature than above-mentioned scope the low or above-mentioned scope of time ratio in short-term, the phenomenon that chemical propertys such as hydrolytic resistance descend sometimes.
All rerum naturas of＜semiconductive polyimide film 〉
The semiconductive polyimide film that the present invention relates to that obtains like this, owing to before completely solidified, give electroconductibility, so, not only give good electrical characteristic, and the various conditions when making by changing can also be controlled above-mentioned electrical characteristic to polyimide film.The result is, the mechanical characteristics of the semiconductive polyimide film of the present invention that obtains like this is improved, and, can present excellent characteristic such as extensibility rising, therefore, the surface resistivity and the volume resistance of polyimide film are precisely controlled, and the voltage-dependent of resistance value diminishes.
Concrete property to the semiconductive polyimide film that the present invention relates to describes as follows: have resistance value in the semi-conductivity zone, at least, in its electrical characteristic, the sheet resistance value that records under impressed voltage 100V is 10 8Ω/～10 13In the scope of Ω/, the volume resistance value is 10 8Ω cm～10 14In the scope of Ω cm.And the voltage-dependent of these resistance values is little.In addition, particularly give operation,, can improve extensibility and mechanical property by adopting the interpolation of mineral filler in electroconductibility.
About the semiconductive polyimide film that the present invention relates to, give operation with electroconductibility and distinguished, one of characteristic in the cards example is described as follows.Also have, resistance value (sheet resistance value and volume resistance value), extensibility and various mechanical characteristics can adopt known general method to measure, and its measuring method is not particularly limited.
Give in the operation in above-mentioned electroconductibility,, can reach 10 adding the sheet resistance value that records under the 100V voltage for the resulting semiconductive polyimide film of interpolation occasion of implementing mineral filler 10Ω/～10 13In the scope of Ω/, the volume resistance value can reach 10 10Ω cm～10 14In the scope of Ω cm.In this semiconductive polyimide film, the mineral filler that contains 15 weight %～50 weight % is preferred.In other words, the weight ratio of polyimide and semi-conductivity mineral filler reach 85: 15～50: 50 semiconductive polyimide film is preferred.
Give in the operation in above-mentioned electroconductibility, to implementing the resulting semiconductive polyimide film of interpolation occasion of electroconductibility imparting agent, can reach 10 adding the sheet resistance value that records under the 100V voltage 8Ω/～10 12In the scope of Ω/, the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm.
Give operation in above-mentioned electroconductibility, resulting semiconductive polyimide film when forming implementing conducting film is 10 adding the sheet resistance value that records under the 100V voltage 8Ω/～10 12In the scope of Ω/, the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm.
Give in the operation in above-mentioned electroconductibility, respectively to the interpolation of electroconductibility imparting agent or the formation of conducting film, can and use the interpolation of mineral filler, at this moment, the amount of the mineral filler that contains in the semiconductive polyimide film is preferred in the scope of 15 weight %～50 weight %.
In addition, at least, give operation in electroconductibility, when implementing the mineral filler interpolation, the extensibility and the mechanical characteristics of resulting semiconductive polyimide film are as follows.
At first, the tensile elongation of above-mentioned semiconductive polyimide film (extensibility) is at least more than 40%, and is preferred more than 45%, more preferably more than 50%.
In addition, in the mechanical characteristics, the modulus in tension of above-mentioned semiconductive polyimide film is compared when not containing filler, reaches at least more than 1.1 times, more can reach more than 1.3 times, especially can reach more than 1.6 times.
Equally, in the mechanical characteristics, the tearing toughness of above-mentioned semiconductive polyimide film, compare when not containing filler, reach at least more than 1.1 times, more can reach more than 1.2 times, especially can reach more than 1.3 times, its absolute value more than 400g/mm, more can reach more than the 500g/mm at least, especially can reach more than the 600g/mm.
Embodiment
Below by embodiment and comparative example, illustrate in greater detail the present invention, but the present invention is not limited by it, those skilled in the art can carry out various changes, correction and change in not exceeding scope of the present invention.Each embodiment and comparative example are put down in writing respectively by the electroconductibility adding method that electroconductibility is given in the operation.Also have,, measure by following method to the various characteristics of polyimide film.
[sheet resistance value and volume resistance value]
The mensuration of the sheet resistance value of semiconductive polyimide film and volume resistance value, all measuring under the environment, place and carried out the humidity adjustment in 48 hours, the R8340 ultra-high resistance instrument (ULTRA HIGH RESISTANCE METER) that adopts ADVANTEST society to make, remove electricity after 30 seconds, add and read the current value after 30 seconds after the 100V voltage and obtain.
[deviation in the face of resistance value]
Under 100V, measure resistance value, the difference of maximum value and minimum value is made in the face deviation obtain (deviation=maximum value in the face-minimum value).
[anti tear transmission intensity and tensile strength]
The anti tear transmission intensity of resulting polyimide film is measured by ASTM D-1938.Similarly its tensile strength is measured by JIS C-2318.
The interpolation of＜mineral filler 〉
Embodiment 1
With pyromellitic acid anhydride and 4,4 '-the DMF solution 100g of 1: 1 mol ratio synthetic of diamino-diphenyl ether polyamic acid, 18.5 weight % in, add by needle-like titanium oxide filler (the long 5.155 μ m of fiber, Fibre diameter 0.27 μ m; Ishihara Sangyo Kaisha, Ltd.'s system, article number FTL-300, powder resistance 10 8Ω cm) slurry of 6.4g and DMF28g formation is mixed.
Then, in the polyamide acid varnish of this fillers dispersed, mix the solidifying agent that constitutes by acetic anhydride 9g, isoquinoline 99.9 11.4g, DMF15.6g, stirred.After the centrifugation deaeration, the curtain coating coating on aluminium foil of this mixture.From being stirred to deaeration, be cooled to simultaneously below 0 ℃.
The multilayer body of this aluminium foil and polyamic acid solution is heated 250 seconds, the gel-film that obtains having self-supporting in 140 ℃.This gel-film is peeled off from aluminium foil, be fixed on the framework.
This gel-film was respectively heated 1 minute in 200 ℃, 300 ℃, 400 ℃, 450 ℃, make the semiconductive polyimide film (filler content: 28.6 weight %) of thickness 75 μ m.The various rerum naturas of this semiconductive polyimide film are shown in table 1.
Embodiment 2
Except adopting needle-like titanium oxide filler (above-mentioned FTL-300, powder resistance 10 8Ω cm) beyond the 9.6g, operates fully similarly to Example 1, obtain the semiconductive polyimide film (filler content: 37.5 weight %) of thickness 75 μ m.The various rerum naturas of this semiconductive polyimide film are shown in table 1.
Reference example
Except not adopting the slurry that constitutes by titanium oxide and DMF, operate fully similarly to Example 1, obtain the polyimide film of thickness 75 μ m.The various rerum naturas of this polyimide film are shown in table 1.
Comparative example 1
Except needle-like titanium oxide (the long 2.86 μ m of fiber, the Fibre diameter 0.21 μ m that adopts the tin indium oxide lining; Ishihara Sangyo Kaisha, Ltd.'s system, FT-2000, powder resistance 10 Ω cm) beyond the slurry that constitutes of 6.4g and DMF28g, operation fully similarly to Example 1 obtains the polyimide film (filler content 28.6%) of thickness 75 μ m.The various rerum naturas of this polyimide film are shown in table 1.
Comparative example 2
Beyond the slurry that constitutes except needle-like titanium oxide (above-mentioned FT-2000, the powder resistance 10 Ω cm) 4.8g that adopts the tin indium oxide lining and DMF28g, operation fully similarly to Example 1 obtains the polyimide film (filler content 23.1%) of thickness 75 μ m.The various rerum naturas of this polyimide film are shown in table 1.
Comparative example 3
Except adopting needle-like titanium oxide (the above-mentioned FT-2000 of tin indium oxide lining, powder resistance 10 Ω cm) beyond 4.8g and the slurry that constitutes with the spherical titanium oxide 2.4g and the DMF28g of tin indium oxide lining, operate fully similarly to Example 1, obtain the polyimide film (filler content 28.6%) of thickness 75 μ m.The various rerum naturas of this polyimide film are shown in table 1.
Comparative example 4
Except adopting spherical titanium oxide (the median size 0.3 μ m of tin indium oxide lining; Ishihara Sangyo Kaisha, Ltd.'s system, ET-600W, powder resistance 30 Ω cm) beyond the slurry that constitutes of 6.4g and DMF28g, polyimide film is made in operation fully similarly to Example 1.Yet the physical strength of film is low, and 400 ℃ of calcinings midway, film splits from the fixed position of framework, can't obtain level and smooth polyimide film
Table 1
Shown in the result of table 1, the semiconductive polyimide film that obtains among the present invention, the mensuration voltage-dependent of resistance value is little, and precision good and easily control surface resistance and volume resistance also have good physical strength.
The interpolation of＜electroconductibility imparting agent 〉
In following embodiment 3～5,, also use the interpolation of electroconductibility imparting agent in the interpolation of mineral filler as the electroconductibility adding method.
The adjustment agent of＜electroconductibility imparting agent 〉
Indium formate and formic acid tin (II) are dissolved in N, dinethylformamide, make the number of elements of indium and formic acid tin contain proportional reach 90: 10 ground be mixed with the indium tin oxides film that adds up to 1 weight % (tin indium oxide conversion concentration) form with coating fluid (for ease of explanation, be called for short the ITO film form uses coating fluid).This ITO film is formed with coating fluid as electroconductibility imparting agent solution.
Embodiment 3
Except adopting needle-like titanium oxide filler (above-mentioned FTL-300, powder resistance 10 8Ω cm) beyond the 4.8g, operation obtains gel-film fully similarly to Example 1.The volatile component content of this gel-film is 43%.
This gel-film is peeled off from aluminium foil, is immersed in the ITO film that obtains in the formulation example and forms, adopt extrusion roll with in the coating fluid, remove remaining drop after, be fixed on the framework.
This gel-film was respectively heated 1 minute at 200 ℃, 300 ℃, 400 ℃, 450 ℃, make the semiconductive polyimide film (filler content: 28.6 weight %) of thickness 75 μ m.The various rerum naturas of this semiconductive polyimide film are shown in table 2.
Also have, in the present embodiment, the imidization rate of just not adding the resulting gel-film of mineral filler is 92%.
Embodiment 4
Except adopting needle-like titanium oxide filler (above-mentioned FTL-300, powder resistance 10 8Ω cm) beyond the 9.6g, operation obtains thickness 75 μ m semiconductive polyimide films (filler content 37.5 weight %) fully similarly to Example 3.The volatile component content of this gel-film is 39%.The various rerum naturas of this semiconductive polyimide film are shown in table 2.
Also have, in the present embodiment, the imidization rate of just not adding the resulting gel-film of mineral filler is 92%.
Embodiment 5
Operation makes the gel-film (mineral filler of use: be above-mentioned FTL-300, powder resistance 10 similarly to Example 4 8Ω cm).This gel-film is immersed in the ITO film that obtains in the formulation example forms with in the coating fluid, remove remaining drop by extrusion roll after, same ITO film is formed be sprayed into (glue spread 10g/m on the gel-film again with coating fluid 2).
This gel-film is fixed on the framework, uses condition similarly to Example 3 to heat, obtain semiconductive polyimide film.The various rerum naturas of this semiconductive polyimide film are shown in table 2.
Also have, in the present embodiment, the imidization rate of just not adding the resulting gel-film of mineral filler is 92%.
Comparative example 5
Form with in the coating fluid except not being immersed in the ITO film,, obtain polyimide film with the same fully operation of embodiment 1.The various rerum naturas of this polyimide film are shown in table 2.
Table 2
As can be known from the results of Table 2, the semiconductive polyimide film that obtains among the present invention is in the semi-conductivity zone, but volume resistance value and sheet resistance value all precision well and are easily controlled, in addition, the voltage-dependent of above-mentioned each resistance value is little, and the resistance value deviation in the face is also little simultaneously.
The formation of＜conducting film 〉
In the following example 6,, in adding, mineral filler also uses the formation of conducting film as the electroconductibility adding method.Also have, form as conducting film and use coating fluid, can use ITO film formation coating fluid by the formulation example preparation of electroconductibility imparting agent.
Embodiment 6
With pyromellitic acid anhydride and 4, among the DMF solution 100g of 1: 1 mol ratio synthetic of 4 '-diamino-diphenyl ether polyamic acid, 18.5 weight %, add by needle-like titanium oxide filler (above-mentioned FTL-300, powder resistance 10 8Ω cm) slurry that constitutes of 3.5g and DMF28g, add the ITO film of preparing in the formulation example form with coating fluid (poly-polyimide: 34g tin indium oxide=100: 2), mixed.
Then, with embodiment 1 complete same operating, obtain gel-film.The volatile component content 43% of this gel-film.This gel-film is peeled off from aluminium foil, and be fixed on the framework.
This gel-film was respectively heated 1 minute in 200 ℃, 300 ℃, 400 ℃, 450 ℃, make the semiconductive polyimide film (filler content: 17 weight %) of thickness 75 μ m.The various rerum naturas of this semiconductive polyimide film are shown in table 3.
Also have, in the present embodiment, not adding the imidization rate that mineral filler and ITO film form with the resulting gel-film of coating fluid is 92%.
Comparative example 6
Form with the coating fluid except not adding the ITO film,, obtain polyimide film with embodiment 6 complete same operating.The various rerum naturas of this polyimide film are shown in table 3.
Table 3
As can be known from the results of Table 3, the semiconductive polyimide film that the present invention obtains is in the semi-conductivity zone, but volume resistance value and sheet resistance value all precision well and are easily controlled, in addition, the voltage-dependent of above-mentioned each resistance value is little, and face internal resistance value deviation is also little simultaneously.
As mentioned above, semiconductive polyimide film of the present invention, its formation be the content weight ratio as polyimide that must composition and semi-conductivity mineral filler be 85: 15～50: 50 (in other words, the content of semi-conductivity mineral filler is 15～50 weight %) polyimide film, the sheet resistance value that records under impressed voltage 100V is 10 10Ω/～10 13In the scope of Ω/, volume resistance is 10 10Ω cm～10 14Ω cm.
Above-mentioned semiconductive polyimide film, its anti-extensibility of opening also has at least more than 40%, and tensional modulus of elasticity and anti tear transmission intensity are for the person more than 1.1 times of the polyimide film that do not contain the semi-conductivity mineral filler is preferred.In addition, above-mentioned semi-conductivity mineral filler is preferred for needle-like person, and the material of semi-conductivity mineral filler is preferred for the titanium oxide person.
In addition, the manufacture method of the semiconductive polyimide film that the present invention relates to, this method comprises: in the homodisperse slurry of semi-conductivity mineral filler, make the polyamic acid solution that contains the semi-conductivity mineral filler by polymerization, make the film making solution curtain coating, the film forming on base material that contain this solution, this film is carried out the manufacturing processed of imidization by heat or chemical method; Or, the solution of polyamic acid and the homodisperse slurry of semi-conductivity mineral filler are mixed, make this mixed solution curtain coating, film forming on base material, this film is carried out the manufacturing processed of imidization by heat or chemical method.
According to the present invention, the semiconductive polyimide film of making, it has resistance value in the semi-conductivity zone, and the mensuration voltage-dependent of resistance value is little, accurately and easily control surface resistance and volume resistance, and can make semiconductive polyimide film with good physical strength.
In addition, the manufacture method of the semiconductive polyimide film that the present invention relates to, as mentioned above, can be partly solidified and/or part exsiccant gel-film to be flooded and/or be coated on the metal conductive oxide film to form with in the coating fluid, then, residual amido acid is carried out imidization, and the method for dry this film.
By the semiconductive polyimide film that the present invention relates to that aforesaid method obtains, the sheet resistance value that records under impressed voltage 100V is 10 8Ω/～10 12In the scope of Ω/, and the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm.
Perhaps, the manufacture method of the semiconductive polyimide film that the present invention relates to, as mentioned above, also can be to form film making solution with coating fluid containing the organic solvent solution of polyamic acid and metal conductive oxide film, delay at the supporter upper reaches and carry out imidization and exsiccant method in addition.
By the semiconductive polyimide film of the present invention that aforesaid method obtains, the sheet resistance value that records under impressed voltage 100V is 10 8Ω/～10 12In the scope of Ω/, and the volume resistance value is 10 8Ω cm～10 13In the scope of Ω cm.
In above-mentioned any method, it is that solution or the dispersion liquid that contains tin indium oxide is that preferably the mineral filler that above-mentioned gel-film or film making solution contain the 15 weight %～50 weight % of the polyimide film of final solid state is preferred that above-mentioned metal conductive oxide film forms with coating fluid.In addition, the semi-conductivity mineral filler is that titanium oxide whisker is preferred.
According to the present invention, in the semi-conductivity zone, but volume resistance value and sheet resistance value precision are good and easily controlled.Yet, resulting semiconductive polyimide film, the voltage-dependent of above-mentioned each resistance value is little, and the resistance value deviation in the face is little simultaneously.
Also have, be used for implementing specific embodiments or the embodiment that preferred plan project of the present invention proposes, be used to illustrate technology contents of the present invention, explanation that can not narrow sense is only limited to these concrete examples, in spirit of the present invention and following claim scope, can implement various changes.
Industrial applicibility
Therefore, according to the present invention, can provide a kind of sheet resistance and volume resistance well to control , the voltage-dependent of these resistance values is little, that mechanical strength is good, can realize high elongation Polyimide film. The result is, the present invention is not only for the manufacture of the chemical industry of polyimide film, and, Also can be used for adopt electric, electronic industry and the mechanical industry of semiconductive polyimide film.

Claims (5)

1. a semiconductive polyimide film wherein, contains the semi-conductivity mineral filler in 15 weight %～50 weight % scopes, and is applying the sheet resistance value that records under the 100V voltage 10 10Ω/mouth～10 13In the scope of Ω/mouth, the volume resistance value is 10 10Ω cm～10 14In the scope of Ω cm, above-mentioned semi-conductivity mineral filler is, with the mineral filler of drying regime at 100kg/cm 2The formed body of pressure lower compression moulding, its volume specific resistance is 10 5～10 9The filler of Ω cm.
2. according to the semiconductive polyimide film described in the claim 1, its tensile elongation is more than 40%.
3. according to the semiconductive polyimide film described in the claim 1, wherein, modulus in tension and tear propagation strength be not for containing more than 1.1 times of polyimide film of above-mentioned semi-conductivity mineral filler.
4. according to the semiconductive polyimide film described in the claim 1, wherein, the semi-conductivity mineral filler be shaped as needle-like.
5. according to the semiconductive polyimide film described in the claim 1, wherein, the material of above-mentioned semi-conductivity mineral filler is a titanium oxide.
CN200610138831A 2001-06-15 2002-06-14 Semiconductive polyimide film and process for production thereof Expired - Lifetime CN100580014C (en)

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