TW201741370A - Polyimide film and process for producing same - Google Patents

Abstract

The present invention addresses the problem of: providing a polyimide film that has satisfactory transportability and has little plane-direction unevenness in haze; and providing a process for producing the polyimide film. The process of the present invention is for producing a polyimide film comprising fine inorganic particles and a polyimide which dissolves in 100 g of dimethylacetamide or 100 g of [gamma]-butyrolactone at 60 DEG C in an amount of 1 g or larger, and is characterized by comprising: a step in which a mixture comprising the polyimide and the fine inorganic particles is prepared; a step in which a dope comprising the mixture, the polyimide, and a solvent is prepared; a step in which the dope is cast on a support to form a film; a step in which the film is separated from the support; and a drying step in which the separated film is dried.

Description

Polyimide film and method of producing the same

The present invention relates to a polyimide film and a method for producing the same, and more particularly to a polyimide film having good transportability and having a low variation in haze value in the plane direction and Its manufacturing method.

Image display devices have been increasing in size. In recent years, in particular, the size of television projectors has increased, so that it is often necessary to require a flexible television projector when moving into a room, or a television projector (flexible television projector) that can be stored in a curled state when not in use. In addition, the demand for curved TV projectors (Curve TV) is increasing.

In addition, for medium-sized image display devices or small-sized image display devices for portable use, the demand for image display devices that can be carried in a folded manner is also increasing. Therefore, the demand for flexible display devices of these image display devices is also increasing.

Polyimide has been found to be useful as the above-mentioned flexible display because it has excellent flex resistance or high modulus of elasticity (for example, refer to Non-Patent Document 1).

Further, as the size of the display has increased, the film has been sought to be wider and rectangular.

However, when the polyimide film is rounded and wound into a roll shape, there is a problem of sticking between the films, which may cause deterioration in conveyability and defects in the film surface to cause flatness deterioration. .

In order to prevent sticking, it has been considered to add inorganic fine particles to increase the smoothness. However, when inorganic fine particles are added to a polyimide film, when the turbidity of the film is easily increased, it is likely to be increased compared with other resins. Produces problems that are not suitable for use as a display.

Further, there are mainly two methods for producing a polyimide film. The first method is to form a film by allowing a solution of a polyamidoline-based compound of a polyamidoamine precursor to be formed on a support, and then performing a ring closure reaction on the support to obtain a desired polyamine. The method of film. The second method is to carry out a ring closure reaction of polylysine in a liquid adjusting tank to obtain a polyamidamide resin (hereinafter, also referred to as soluble polyamidamine) which is soluble in a solvent, and then dissolve the solvent. A method in which a polymethyleneamine resin is redissolved in a solvent and allowed to flow on a support to obtain a polyimide film (for example, refer to Patent Document 1).

In the method of allowing the solution of the former polyamic acid-based compound to be carried out on the support, the reaction of the closed-loop reaction is carried out after the flow is carried out on the support, and the step of high-temperature treatment of the film is necessary. However, the method of using the latter of the soluble polyamidamide resin does not have a step of performing high-temperature treatment of the film as in the former because the ring-closing reaction is carried out in the reaction solution. Therefore, it can correspond to the high plane required for display use. The balance of sexual or optical properties.

Among them, the inventors of the present invention conducted various studies on a method of producing a long roll by mixing inorganic fine particles in a soluble polyamidamine film.

However, when a long roll is produced by mixing inorganic fine particles in a soluble polyimine film, it is found that a turbidity deviation occurs in the direction of the film surface, and the standard deviation of the turbidity value is increased, etc., using soluble polytheneamine. A problem unique to the film produced.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2015-021022

[Non-patent literature]

[Non-Patent Document 1] NHK Technology Research Institute "R & D/No.145" 2014.5 p12-15

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a solution to the problem is to provide a good transportability when the long film is wound into a roll shape, and the haze value of the film in the surface direction is low. Deviated polythene film. A method of producing the polyamidamine film is also provided.

In order to solve the above problems of the present invention, in the course of studying the causes of the above problems, it has been found that a mixture of mixed soluble polyamidos and inorganic fine particles is prepared in advance, and the mixture is mixed with a new soluble polyamine. The dopant can be subjected to a flow of the solution to obtain a polyimide film having good transportability and a low turbidity value in the surface direction of the film, and thus the present invention has been completed.

That is, the problem of the present invention can be solved by the following means.

A method for producing a polyimide film, which comprises dissolving 1 g or more of polymethyleneamine and inorganic fine particles with respect to 100 g of dimethylacetamide or 100 g of γ-butyrolactone at 60 ° C. A method for producing a polyimide film, comprising the steps of: preparing a mixture containing the polyimine and the inorganic fine particles, and preparing a dopant containing the mixture and the polyamine and a solvent; a step of forming a film by stretching the dopant onto the support, a step of peeling the film from the support, and a drying step of drying the film after peeling.

2. The method for producing a polyimide film according to the above aspect, wherein the mixture is a crushed product obtained by crushing a polyimine film containing the polyimine and the inorganic fine particles.

3. The method for producing a polyimide film according to the above aspect, wherein the mixture contains a dopant of the polyimine and the inorganic fine particles and a solvent.

4. The method for producing a polyimide film according to any one of the items 1 to 3, wherein the mixture contains 10 to 70 masses based on the obtained polyimide film. % of the mass ratio.

A polyamidamine film which is characterized in that it contains at least 1 g of polyimide and inorganic fine particles with respect to 100 g of dimethylacetamide or 100 g of γ-butyl lactone at 60 ° C, and The standard deviation of the haze value in the plane direction is 1 or less.

According to the above means of the present invention, it is possible to provide a polyimide film which has good film transportability and a low variation in haze value in the surface direction of the film. A method of producing the polyamidamine film is also provided.

Although the mechanism of action of the effect of the present invention to the mechanism of action is not completely clear, it is presumed to be the following.

In the method for producing a polyamimid film in which a polyaminic acid is subjected to a solution-draining method, it is presumed that a ring-closing reaction has not been completed at the time of the precipitation, so that a chemical reaction is formed at the time of film formation. Therefore, the resin is easily formed into an alignment by the reaction, and the inorganic particles can be formed into a film in a relatively uniform distribution state between the resin molecular chain and the gap of the resin molecular chain.

However, in the method for producing a polyimide film using a soluble polyamidamine, it is presumed that the chemical structure of the closed-loop polyamine is formed at the time of the extension, so that the resin is more difficult to form an alignment when the flow is extended. It is easily affected by the chemical composition such as the polarity of the resin. Therefore, the mixed inorganic fine particles are prone to shift, and the turbidity is likely to occur in the plane direction. difference.

In the present invention, in order to prepare a mixture obtained by mixing inorganic fine particles in a soluble polyimide, and mixing it with a new soluble polyamine, a dopant is prepared, and then a flow is carried out. It is presumed that the inorganic fine particles are mixed with the soluble polyamidamide resin in advance by mixing the inorganic fine particles in the soluble polyamidamine, so that the new soluble polyamidoamine is more easily combined, so even the flow is allowed to flow. The new soluble polyamines form an alignment, but the migration of inorganic microparticles is also less. Therefore, the deviation of the turbidity in the direction of the surface of the film is also small.

As described above, a mixture prepared by mixing inorganic fine particles in a soluble polyiminamide is prepared, and then mixed with a new soluble polyamidamine to prepare a dopant, and then the flow is carried out. In the soluble polyamidide thin film technique, a polyimide film having a standard deviation of a haze value in the plane direction of 1 or less is first obtained.

[Formation of the Invention]

The method for producing a polyamidamine film of the present invention comprises a method of dissolving polyglycolide and inorganic fine particles of 1 g or more with respect to 100 g of dimethylacetamide or 100 g of γ-butyrolactone at 60 ° C. A method for producing a melamine film, characterized by comprising

Preparing a step of preparing a mixture containing the mixture of the polyiminamide and the inorganic fine particles, preparing a dopant containing the mixture and the polyamine and the solvent, and allowing the dopant to be formed on the support to form a film a step of peeling the film from the support, and drying the film after peeling A method for producing a polyimide film of a drying step. This feature is a common technical feature in the invention of each claim.

In the embodiment of the present invention, the mixture is a crushed product obtained by crushing a polyimine film containing the polyimine and the inorganic fine particles, and the deviation of the turbidity value in the plane direction is small. The point of view is preferred.

Moreover, it is preferable that the mixture contains a dopant of the polyimide and the inorganic fine particles and a solvent, and the difference in the haze value in the plane direction is small.

In addition, it is preferable that the mixture has a mass ratio of 10 to 70% by mass with respect to the obtained polyimide film, and the difference between the transportability and the haze value in the plane direction is preferable.

Hereinafter, the present invention and its constituent elements, and aspects of the invention will be described in detail. In addition, in the present application, "~" is a user who includes the numerical values described before and after the lower limit value and the upper limit value.

<Summary of Polyimine Film of the Present Invention>

The polyamidamine film of the present invention is a polyimine film containing a soluble polyamidamine as a main component. The solubility is based on 100 g of dimethylacetamide or 100 g of γ-butyrolactone at 60 ° C, preferably 1 g or more.

In the present invention, the term "polyimine" as a main component means that the total amount of polyamidene in the film is 50% by mass or more. It is preferably 80% by mass or more.

<polyamidamine>

The polymethyleneamine of the present invention is a resin having a quinone imine structure (hereinafter, also referred to as a polyarylene resin), and a resin containing a quinone bond in a repeating unit. The polyamine is preferably formed from a diamine or a derivative thereof and an acid anhydride or a derivative thereof.

The polyimine of the present invention may, for example, be a polyamidoamine, a polyamidimide, a polyether quinone, or a polyester phthalate having a structure represented by the following formula (1.1). Amines, etc.

(1) Polyimine having a structure represented by formula (1.1) (1.1) Structure of the anhydride side

The polyiminamide which can be used in the present invention is particularly preferably a polyarylene which has a repeating unit represented by the following formula (1.1).

In the formula (1.1), R represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring, or a tetravalent aliphatic hydrocarbon group or an alicyclic hydrocarbon group having 4 to 39 carbon atoms. A represents a divalent aliphatic hydrocarbon group having 2 to 39 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by the combination thereof, and may further contain -O-, -SO ₂ -, -CO At least one selected from the group consisting of -, -CH ₂ -, -C(CH ₃ ) ₂ -, -OSi(CH ₃ ) ₂ -, -C ₂ H ₄ O-, and -S- as a bond base.

An aromatic hydrocarbon ring represented by R, for example, an anthracene ring, a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, a phenanthrene ring, an anthracene ring, a 1,2-benzophenanthrene ring, a tetracene ring, Triphenylene ring, o-terphenyl ring, m-triphenyl ring, p-triphenyl ring, acenaphthene ring, coronene ring, fluoranthene ring, tetracene ring, pentacene ring, fluorene Ring, 2,3,6,7-dibenzophenanthrene ring, anthracene ring, anthraquinone ring, skin ring, anthonyne ring, etc.

Further, in the same manner, an aromatic heterocyclic ring represented by R, for example, a siloles ring, a furan ring, a thiophene ring, an oxazole ring, a pyrrole ring, a pyridine ring, or an anthracene Ring, pyrimidine ring, pyridyl Ring, three Ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, anthracene ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinolin Oxazoline ring a ring, a Thienothiophene ring, a carbazole ring, an azaindazole ring (any one or more of the carbon atoms constituting the carbazole ring is substituted by a nitrogen atom), a dibenzosilole ring, a dibenzofuran ring, a dibenzothiophene ring, a benzothiophene ring or a ring of any one or more of the carbon atoms constituting the dibenzofuran ring, which is substituted by a nitrogen atom, a benzodifuran ring, a benzodithiophene ring , acridine ring, benzoquinoline ring, brown Ring, phenanthridine ring, phenanthroline ring, ring 吖 (cyclazine) ring, quinoline ring, Thebenidine ring, quinindoline ring, triphenyldithiazide Ring, triphenyl dioxine Ring, Phenanthrazine ring, 蒽 (anthrazine) ring, perimidine ring, naphthofuran ring, naphthylthiophene ring, naphthalene difuran ring, naphthalene dithiophene ring, furfuran ring, fluorene furan ring, thiophene ring, quinone dithiophene ring, thioindole ring , phenothiazine, dibenzoxazole ring, carbazole ring, dithienobenzene and the like.

The tetravalent aliphatic hydrocarbon group having 4 to 39 carbon atoms represented by R, for example, butane-1,1,4,4-tetrayl-yl, octane-1,1,8,8-tetrayl a group of a group, a decane-1, a 1,10,10-tetrayl- group or the like.

Further, the tetravalent alicyclic hydrocarbon group having 4 to 39 carbon atoms represented by R may, for example, be cyclobutane-1,2,3,4-tetrayl-yl or cyclopentane-1, 2, 4 ,5-tetraki-yl, cyclohexane-1,2,4,5-tetrayl-yl, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetrayl-yl, Bicyclo[2.2.2]octane-2,3,5,6-tetrayl-yl, 3,3',4,4'-dicyclohexyltetraki-yl, 3,6-dimethylcyclohexane a group of -1,2,4,5-tetraki-yl, 3,6-diphenylcyclohexane-1,2,4,5-tetrayl-yl or the like.

The divalent aliphatic hydrocarbon group having 2 to 39 carbon atoms, which may or may not have the above-mentioned bonding group, may be, for example, a group represented by the following structural formula.

In the above structural formula, n represents the number of repeating units, preferably 1 to 5, and preferably 1 to 3. Also, X is a carbon number of 1 to 3 The base, that is, the methyl group, the ethyl group, the trimethyl group, the propane-1,2-diyl group, and the methyl group is preferred.

The divalent alicyclic hydrocarbon group having 2 to 39 carbon atoms, which may or may not have the above-mentioned bond group, may be, for example, a group represented by the following structural formula.

The aromatic hydrocarbon group having a carbon number of 2 to 39 and having the above bond group represented by Φ may be, for example, a group represented by the following structural formula.

The group formed by the combination of the aliphatic hydrocarbon group, the alicyclic hydrocarbon group and the aromatic hydrocarbon group represented by A may, for example, be a group represented by the following structural formula.

The base represented by A, for example, the number of carbons having a bonding group The divalent aromatic hydrocarbon group of 2 to 39 is preferably a combination of the aromatic hydrocarbon group and the aliphatic hydrocarbon group, and particularly preferably a group represented by the following structural formula.

The acid anhydride used in the present invention is preferably a derivative of a carboxylic anhydride, an aliphatic or an alicyclic tetracarboxylic acid, for example, an aliphatic or alicyclic tetracarboxylic acid ester, an aliphatic or alicyclic tetracarboxylic acid Anhydride, etc. Further, among the aliphatic or alicyclic tetracarboxylic acids or derivatives thereof, an alicyclic tetracarboxylic dianhydride is preferred.

Further, the derivative means a compound which is changed to an aliphatic or alicyclic tetracarboxylic acid. For example, when it is an aliphatic tetracarboxylic dianhydride, a compound having two carboxyl groups may be suitably used instead of the anhydrate. a compound in which one or both of the carboxyl groups are esterified, or an acid chloride in which one or both of the two carboxyl groups are chlorinated.

High heat resistance can be obtained by using these antimony compounds And a polyimide film having excellent optical properties and a low coloration (yellowing).

An aliphatic tetracarboxylic acid, for example, 1,2,3,4-butanetetracarboxylic acid or the like. An alicyclic tetracarboxylic acid, for example, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid and the like.

The aliphatic tetracarboxylic acid ester is, for example, a monoalkyl ester, a dialkyl ester, a trialkyl ester or a tetraalkyl ester of the above aliphatic tetracarboxylic acid. The alicyclic tetracarboxylic acid ester is, for example, a monoalkyl ester, a dialkyl ester, a trialkyl ester or a tetraalkyl ester of the above alicyclic tetracarboxylic acid. Further, the alkyl moiety is preferably an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms.

The aliphatic tetracarboxylic dianhydride is, for example, 1,2,3,4-butanetetracarboxylic dianhydride or the like. An alicyclic tetracarboxylic dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, 1,2,4 , 5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2,3 , 5,6-tetracarboxylic dianhydride, and the like. Particularly preferred is 1,2,4,5-cyclohexanetetracarboxylic dianhydride. In general, as the constituent component of the aliphatic diamine, the polyamine of the intermediate product forms a strong salt due to the polyamine of the intermediate product, and therefore, when the polymer is to be polymerized, the solubility of the salt is higher. A high solvent (e.g., cresol, N,N-dimethylacetamide, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) is preferred. Among them, as a constituent component of the aliphatic diamine, when it is a constituent of 1,2,4,5-cyclohexanetetracarboxylic dianhydride, the salt of polyglycine and diamine is Since it is connected by a weak bond, it is easy to carry out high molecular weight, and it is easy to produce a flexible film.

Others, for example, 4,4'-diphthalic anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,3,3',4'-biphenyltetracarboxylate can be used. Acid dianhydride, 4,4'- oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylate Acid dianhydride, 4-(2,5-dioxatetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 5-(2,5-dioxo Heterotetrahydrofuranyl-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 3,4'-oxo Diphthalic anhydride, 3,4,9,10-decanetetracarboxylic dianhydride (PIGMENT RED 224) 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylate Acid dianhydride tricyclo [6.4.0.0 ^2,7 ] dodecane-1,8:2,7-tetracarboxylic dianhydride and the like.

Further, an acid anhydride having an anthracene skeleton or a derivative thereof can also be used. It has the effect of improving the specific coloration of polyamidoamine. An acid anhydride having an anthracene skeleton, for example, 9,9-bis(3,4-dicarboxyphenyl)decanoic acid dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)benzene can be used. And hexanoic acid dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)-3-phenylphenyl]nonanoic acid dianhydride, and the like.

The aromatic, aliphatic or alicyclic tetracarboxylic acid or a derivative thereof may be used alone or in combination of two or more. Further, other tetracarboxylic acids or derivatives thereof (especially two may be used in combination as long as they do not impair the solvent solubility of polyamine, the flexibility of the polyimide film, the hot pressability, and the transparency. anhydride).

Other tetracarboxylic acids or derivatives thereof, for example, pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 2,2-bis(3,4-dicarboxyphenyl)- 1,1,1,3,3,3-hexafluoropropane, 2,2-bis(2,3- Dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, bis(3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)ether, bis ( 2,3-dicarboxyphenyl)ether, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 4,4 -(p-phenylene dioxy)dicarboxylic acid, 4,4-(m-phenylenedioxy)dicarboxylic acid, 1,1-bis(2,3-dicarboxyphenyl)ethane An aromatic tetracarboxylic acid such as bis(2,3-dicarboxyphenyl)methane or bis(3,4-dicarboxyphenyl)methane and derivatives thereof (especially dianhydride); An aliphatic tetracarboxylic acid having a carbon number of 1 to 3 such as a tetracarboxylic acid or the like and a derivative thereof (particularly a dianhydride).

The acid dianhydride may be 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride or biphenyltetracarboxylic dianhydride, which has excellent transparency and is easily subjected to heat shrinkage. The idea of thermal correction is better.

The repeating unit represented by the above formula (1.1) is preferably from 10 to 100 mol%, more preferably from 50 to 100 mol%, still more preferably from 80 to 100 mol%, based on the total repeating unit. Good is 90~100%. Further, the number of repeating units of the formula (1.1) in the polyimidamine 1 molecule is from 10 to 2,000, preferably from 20 to 200, and in this range, the glass transition temperature (Tg) is 230 to 350. °C is preferred, preferably 250~330 °C.

(1.2) Structure of the side of the diamine

The diamine or a derivative thereof is preferably an aromatic diamine or an isocyanate, and the like, and an aromatic diamine is preferred.

The diamine or a derivative thereof used in the present invention, for example, an aromatic diamine, an aliphatic diamine or a mixture thereof may be used, but the aromatic diamine may inhibit the polyamidide film. Whitening point of view Preferably.

Further, the "aromatic diamine" in the present invention means a diamine in which an amine group is directly bonded to an aromatic ring, and a part of the structure may contain an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and other substituents. (for example, a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.). The "aliphatic diamine" is a diamine in which an amine group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and a part of the structure may contain an aromatic hydrocarbon group or another substituent (for example, a halogen atom, Sulfonyl, carbonyl, oxygen atom, etc.).

Examples of the aromatic diamine, for example, p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-toluidine, m -toluidine, bis(trifluoromethyl)benzidine, hexafluorobenzidine, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4, 4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,6 -diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenyl hydrazine, 3,4'-diaminodiphenyl hydrazine, 4,4'-diaminobenzophenone, 2,2-bis(4-(4- Aminophenoxy)phenyl)propane, 2,2-bis(4-(2-methyl-4-aminophenoxy)phenyl)propane, 2,2-bis(4-(2,6) -Dimethyl-4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4- (2-methyl-4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(2,6-dimethyl-4-aminophenoxy)phenyl)6 Fluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(2-methyl-4-aminophenoxy)biphenyl, 4,4 '-Bis(2,6-dimethyl-4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis(4-(4-amino) Phenoxy)phenyl)indole, bis(4-(2-methyl-) 4-aminophenoxy)phenyl)indole, bis(4-(2,6-dimethyl-4-aminophenoxy)phenyl)indole, bis(4-(4-aminophenoxy) Phenyl)ether, bis(4-(2-methyl-4-aminophenoxy)phenyl)ether, bis(4-(2,6-dimethyl-4-aminophenoxy) Phenyl)ether, 1,4-bis(4-aminophenoxy)benzene, 1,4-bis(2-methyl-4-aminophenoxy)benzene, 1,4-bis(2) ,6-Dimethyl-4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(2-methyl-4-aminophenoxyl) Benzo, 1,3-bis(2,6-dimethyl-4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 2,2-bis (2) -Methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-ethyl-4-aminophenyl) ) propane, 2,2-bis(3,5-dimethyl-4-aminophenyl)propane, 2,2-bis(2,6-dimethyl-4-aminophenyl)propane, 2 , 2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(2-methyl-4-aminophenyl)hexafluoropropane, 2,2-bis(2,6-dimethyl 4-aminophenyl)hexafluoropropane, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, α,α'-bis(2-methyl- 4-aminophenyl)-1,4-diisopropylbenzene, α,α'-bis(2,6-dimethyl-4-aminophenyl)-1,4- Diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,4-diisopropylbenzene, α,α'-bis(4-aminophenyl)-1,3- Diisopropylbenzene, α,α'-bis(2-methyl-4-aminophenyl)-1,3-diisopropylbenzene, α,α'-bis(2,6-dimethyl 4-aminophenyl)-1,3-diisopropylbenzene, α,α'-bis(3-aminophenyl)-1,3-diisopropylbenzene, 1,1-double ( 4-aminophenyl)cyclopentane, 1,1-bis(2-methyl-4-aminophenyl)cyclopentane, 1,1-bis(2,6-dimethyl-4-amine Phenyl)cyclopentane, 1,1-bis(4-aminophenyl)cyclohexane, 1,1-bis(2-methyl-4-aminophenyl)cyclohexane, 1,1 - bis(2,6-dimethyl-4-aminophenyl)cyclohexane, 1,1-bis(4-aminophenyl)4-methyl-cyclohexane, 1,1-double ( 4-aminophenyl)norbornane, 1,1-bis(2-methyl-4-aminophenyl)norbornane, 1,1-bis(2,6-dimethyl-4-amine base Phenyl)norbornane, 1,1-bis(4-aminophenyl)adamantane, 1,1-bis(2-methyl-4-aminophenyl)adamantane, 1,1-double ( 2,6-Dimethyl-4-aminophenyl)adamantane, 1,4-phenylenediamine, 3,3'-diaminobenzophenone, 2,2-bis(3-amino group Phenyl) hexafluoropropane, 3-aminobenzylamine, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy) Benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(3-aminophenoxy)phenyl]anthracene, 1,3-bis[2] -(4-Aminophenyl)-2-propyl]benzene, bis(2-aminophenyl) sulfide, bis(4-aminophenyl) sulfide, 1,3-bis(3-amine Propyl)tetramethyldioxane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4 '-Ethyl diphenylamine, 4,4'-extended methyl bis(cyclohexylamine), 4,4'-extended methyl bis(2,6-diethylaniline), 4,4'-extension Bis(2-methylcyclohexylamine) and the like.

Aliphatic diamines, for example, ethylidene diamine, hexamethyldiamine, polyethylene glycol bis(3-aminopropyl)ether, polypropylene glycol bis(3-aminopropyl)ether, 1, 3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, m-xylenediamine, p-xylenediamine, 1,4-bis(2-amino group) -isopropyl)benzene, 1,3-bis(2-amino-isopropyl)benzene, isophoronediamine, norbornanediamine, nonanediamine, 4,4'-diamine Dicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 2,3-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,5 - bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)-bicyclo[2.2.1]heptane, 2,2-bis(4,4'-diamine Base cyclohexyl)propane, 2,2-bis(4,4'-diaminomethylcyclohexyl)propane, and the like.

Further, a diamine or a derivative thereof having an anthracene skeleton for the purpose of improving the specific coloration of polybenzamine can also be used. For example, 9,9-bis[4-(4-aminophenoxy)phenyl]anthracene, 9,9-bis[4-(4-aminophenoxy)-3-phenylphenyl]indole 9,9-bis[4-(3-aminophenoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(2-aminophenoxy)-3-phenyl Phenyl]anthracene, 9,9-bis[4-(4-amino-3-methylphenoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(4-amino) -2-methylphenoxy)-3-phenylphenyl]anthracene, 9,9-bis[4-(4-amino-3-ethylphenoxy)-3-phenylphenyl]indole Wait.

Also, it is also possible to use the three represented by the following formula A diamine compound of the mother nucleus.

With three In the diamine compound of the above formula of the parent nucleus, R ¹ represents a hydrogen atom or an alkyl group or an aryl group having 1 to 12 carbon atoms (preferably having a carbon number of 1 to 10, particularly preferably a carbon number of 1 to 6), and R ^{2 .} The alkyl group or the aryl group having 1 to 12 carbon atoms (preferably, the carbon number is 1 to 10, particularly preferably the carbon number is 1 to 6), and R ¹ and R ² may be different or the same.

The alkyl or aryl group having 1 to 12 carbon atoms of R ¹ and R ² may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group. Base, phenyl, benzyl, naphthyl, methylphenyl, biphenyl, and the like.

Connection three The two NH-based aminoanilinyl groups in the 4-aminoanilino group or the 3-aminoanilino group may be the same or different, and a 4-aminoanilino group is preferred.

With three The diamine compound represented by the above formula of the mother nucleus, specifically, for example, 2,4-bis(4-aminoanilino)-6-anilino-1,3,5-three , 2,4-bis(3-aminoanilino)-6-anilino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-benzylamino-1,3,5-three , 2,4-bis(3-aminoanilino)-6-benzylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-naphthylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-benzidine-1,3,5-three , 2,4-bis(4-aminoanilino)-6-diphenylamino-1,3,5-three , 2,4-bis(3-aminoanilino)-6-diphenylamino-1,3,5-three 2,4-bis(4-aminoanilino)-6-dibenzylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-dinaphthylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-N-methylanilino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-N-methylnaphthylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-methylamino-1,3,5-three , 2,4-bis(3-aminoanilino)-6-methylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-ethylamino-1,3,5-three , 2,4-bis(3-aminoanilino)-6-ethylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-dimethylamino-1,3,5-three 2,4-bis(3-aminoanilino)-6-dimethylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-diethylamino-1,3,5-three , 2,4-bis(4-aminoanilino)-6-dibutylamino-1,3,5-three 2,4-bis(4-aminoanilino)-6-amino-1,3,5-three , 2,4-bis(3-aminoanilino)-6-amino-1,3,5-three Wait.

The isocyanate of the diamine derivative is, for example, a diisocyanate obtained by reacting the above aromatic or aliphatic diamine with phosgene.

Further, another diamine derivative, for example, a diamino dioxane such as the above aromatic or aliphatic diamine and chlorotrimethylnonane, is obtained by reacting a trimethylsulfonium alkylated aromatic or fat. Group of diamines and the like.

The diamine may be 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, which has a viewpoint of excellent transparency and is easy to be thermally corrected by heat shrinkage. good.

The above diamine and its derivative may be used arbitrarily, and among these, the amount of the diamine is preferably 50 to 100 mol%, and preferably 80 to 100 mol%.

(1.3) Synthesis of polyglycine and oxime imidization (1.3.1) Synthesis of polyaminic acid

Polylysine can be obtained by polymerizing at least one of the above-mentioned tetracarboxylic acids in at least one of the above-mentioned diamines in a suitable solvent.

Further, the polyphthalate is obtained by subjecting the tetracarboxylic dianhydride to an open alcohol by using an alcohol such as methanol, ethanol, isopropanol or n-propanol to diesterify the obtained diester. It can be obtained by reacting with the aforementioned diamine compound in a suitable solvent. Further, the polyphthalate may be obtained by reacting the carboxylic acid group of the polyamic acid obtained above with the above-mentioned alcohol to form an esterification method.

The reaction of the aforementioned tetracarboxylic dianhydride with the aforementioned diamine compound, It can be carried out using previously known conditions. The order of addition or addition of the tetracarboxylic dianhydride and the diamine compound is not particularly limited. For example, a tetracarboxylic dianhydride and a diamine compound can be sequentially introduced into a solvent, and stirred at an appropriate temperature to obtain a polyamic acid.

The amount of the diamine compound is usually 0.8 mol or more, preferably 1 mol or more, based on 1 mol of the tetracarboxylic dianhydride. Further, it is usually 1.2 m or less, preferably 1.1 m or less. When the amount of the diamine compound is within these ranges, the yield of the obtained polylysine can be increased.

The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set in accordance with the reaction conditions or the viscosity of the polyaminic acid solution. For example, the total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass based on the total amount of the solution. Hereinafter, it is preferably 30% by mass or less. When the amount of the reaction substrate is within these ranges, polylysine can be produced at a lower cost and in a good yield.

The reaction temperature is not particularly limited, but is usually 0 ° C or higher, preferably 20 ° C or higher, and usually 100 ° C or lower, preferably 80 ° C or lower. The reaction time is not particularly limited, but is usually 1 hour or longer, preferably 2 hours or longer, and usually 100 hours or shorter, preferably 24 hours or shorter. When the reaction is carried out under these conditions, polylysine can be obtained at a lower cost and in a good yield.

The polymerization solvent used in the reaction, for example, a hydrocarbon solvent such as hexane, cyclohexane, heptane, benzene, toluene, xylene or trimethylbenzene; carbon tetrachloride, dichloromethane, chloroform, 1,2- Dichloroethane, chlorobenzene, dichloro a halogenated hydrocarbon solvent such as benzene or fluorobenzene; an ether solvent such as diethyl ether, tetrahydrofuran, 1,4-dioxane or methoxybenzene; a ketone solvent such as acetone or methyl ethyl ketone; N,N- Amidoxime solvent such as dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone; aprotic such as dimethyl hydrazine or γ-butyrolactone The polar solvent; a heterocyclic solvent such as pyridine, pyridyl, lutidine, quinoline or isoquinoline; a phenol solvent such as phenol or cresol, and the like are not particularly limited. The polymerization solvent may be used alone or in combination of two or more solvents.

The terminal group of the polyamic acid can be arbitrarily selected from the acid anhydride group or the amine group by using any one of the tetracarboxylic dianhydride and the diamine compound in the polymerization reaction.

When the terminal group is an acid anhydride terminal, the acid anhydride terminal can be used without using a subsequent treatment, or a hydrolyzed dicarboxylic acid can be used. Further, an alcohol having 4 or less carbon atoms may be used as the ester. Alternatively, a monofunctional amine compound or an isocyanate compound may be used to seal the ends. The amine compound or the isocyanate compound to be used herein is not particularly limited as long as it is a monofunctional primary amine compound or an isocyanate compound, and can be used. For example, aniline, methylaniline, dimethylaniline, trimethylaniline, ethylaniline, diethylaniline, triethylaniline, aminophenol, methoxyaniline, amine benzoic acid, benzidine, naphthalene Alkylamine, cyclohexylamine, phenylisocyanate, xylene isocyanate, cyclohexyl isocyanate, methylphenylisocyanate, trifluoromethylphenylisocyanate, and the like.

Further, when the terminal group is an amine terminal, it can seal the terminal amine group via a monofunctional acid anhydride, and the amine group is prevented from remaining at the terminal end. The acid anhydride used herein is not particularly limited as long as it forms a monofunctional acid anhydride of a dicarboxylic acid or a tricarboxylic acid upon hydrolysis. For example, maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, succinic anhydride, norbornene dicarboxylic anhydride, 4-(phenylethynyl)phthalic anhydride, 4-ethynylphthalic anhydride , phthalic anhydride, methyl phthalic anhydride, dimethyl phthalic anhydride, trimellitic anhydride, naphthalene dicarboxylic anhydride, 7-oxabicyclo[2.2.1] heptane-2,3-dicarboxyl Anhydride, bicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, 4-oxatricyclo[5.2.2.0 ^{2 , 6} ] undecane-3,5-dione, octahydro-1,3-dioxaisobenzofuran-5-carboxylic acid, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, Dimethylcyclohexanedicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyl-4-cyclohexene-1,2-dicarboxylic anhydride, and the like.

(1.3.2) oxime imidization

Here, the polyamidamine may be a method in which a polylysine solution is heated to imidize a polyphosphonium amide (thermal hydrazide method), or a polycyclic acid solution is added to a closed loop. A catalyst (an imidization catalyst) can be obtained by a method of imidizing polyphosphonium amide (chemical hydrazine imidation method).

Further, a method in which a polyaminic acid solution is heated to imidize a polyphosphonium amide (thermal imidization method), or a poly-phthalic acid solution is added to a closed-loop catalyst a method for imidizing a polyphosphonium amide (chemical ruthenium imidation method), which can form a polyamic acid formed by an acid anhydride and a diamine in a reaction vessel in which polymerization is carried out in a reaction vessel. Niobium imidization is also possible.

In the thermal hydrazine imidation method in the reaction vessel, the polyamic acid in the polymerization solvent is subjected to heat treatment for 0.1 to 200 hours in a temperature range of, for example, 80 to 300 ° C to carry out hydrazine imidization. Further, the temperature range is preferably 150 to 200 ° C, and when the temperature is 150 ° C or higher, the ruthenium imidization can be surely performed. On the other hand, when the temperature is 200 ° C or lower, the solvent or the unreacted raw material can be prevented. The increase in resin concentration caused by oxidation and solvent evaporation.

Further, in the thermal hydrazine imidation method, an azeotropic solvent may be added to the polymerization solvent in view of the fact that the produced water can be efficiently removed in the hydrazine imidization reaction. Examples of the azeotropic solvent include aromatic hydrocarbons such as toluene, xylene, and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and dimethylcyclohexane. When the azeotropic solvent is used, the amount thereof is from about 1 to 30% by mass, preferably from 5 to 20% by mass, based on the total amount of the organic solvent.

Further, in the chemical hydrazine imidation method, a known ring-closing catalyst may be added to the polyamic acid in the polymerization solvent to carry out hydrazine imidization. Specific examples of the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylenediamine, and heterocyclic tertiary amines such as isoquinoline, pyridine and formylpyridine. Further, for example, a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound containing a nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound . In particular, 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 5-methyl Lower alkylimidazole, N-benzyl-2-methylimidazole such as benzimidazole Imidazole derivatives such as oxazole, isoquinoline, 3,5-lutidine, 3,4-dimethylpyridine, 2,5-lutidine, 2,4-dimethylpyridine, 4-n Substituted pyridine such as -propylpyridine or p-toluenesulfonic acid or the like is preferred. The amount of the closed-loop catalyst added is 0.01 to 2 times the equivalent of the glycine acid unit of the poly-proline, and particularly preferably about 0.02 to 1 equivalent. When a closed-loop catalyst is used, the physical properties of the obtained polyamidene are improved, and in particular, the elongation or fracture resistance can be improved.

Further, in the above-described hydrazine imidization method or chemical hydrazylation method, a dehydrating agent may be added to the polyaminic acid solution, for example, an aliphatic acid anhydride such as acetic anhydride or phthalic anhydride. The aromatic acid anhydride or the like may be used singly or in combination. Further, when a dehydrating agent is used, it is preferred to carry out the reaction at a low temperature. Further, when a dehydrating agent is added only to the polyaminic acid solution, the polyphosphonium amide can be imidized. However, since the reaction rate is relatively slow, heating or addition of a ring-closing catalyst is carried out as described above. Aminator is preferred.

In this manner, it is advantageous to carry out the hydrazide-forming polyamine reaction in the reaction vessel, which is less likely to cause hydrolysis and lower the molecular weight during storage.

Further, in the case where the ruthenium imidization reaction is carried out again, in the case of polyarylene which has a ruthenium iodide ratio of 100%, since the hydrazine imidization is not required to be carried out on the film or the film, the drying temperature can be lowered.

Further, the closed polyamine can be reprecipitated and purified by using a poor solvent or the like, dissolved in a solvent, and dried to form a film.

According to this method, the solvent of the polymerization solvent and the solvent can be different, and the properties of the polyimide film can be guided by selecting the most suitable solvent, respectively.

For example, in order to quantify the molecular weight of polylysine, polymerization and ring closure are carried out using dimethylacetamide, followed by curing with methanol, drying, and then forming a solution by using dichloromethane to carry out a solution. When drying, the result is high molecular weight and low temperature drying.

Further, when dichloromethane is used as the solvent, it may be used in combination with other solvents. For example, tetrahydrofuran (THF), dioxane, cyclohexanone, cyclopentanone, γ-butyrolactone, ethanol, methanol, butanol, isopropanol or the like can be used, and a suitable auxiliary solvent can be used.

(1.4) Other polyamines

In addition to the polymethyleneamine, a polymethyleneamine containing an atom such as phosphorus, ruthenium or sulfur may also be used.

For example, the phosphorus-containing polyamidamine can be used, for example, in paragraphs [0010] to [0021] and JP-A-2011-0074177, paragraphs [0011] to [0025], respectively. Polyamine.

For the polyamidamine containing ruthenium, for example, the polyamidene obtained by imidating the polyamidamine precursor oxime described in paragraphs [0030] to [0045] of JP-A-2013-028796 can be used.

As the sulfur-containing polyamine, for example, paragraphs [0009] to [0025] of JP-A-2010-189322, respectively, can be used. JP-A-2008-274234, paragraph [0012]-[0025] and JP-A-2008-274229, paragraph [0012]-[0023], which is obtained by imidating a polyamidamine precursor quinone. Guanamine.

In addition, the alicyclic polyimine described in paragraphs [0008] to [0012] of JP-A-2009-256589, and the paragraph [0008]-[0012] of JP-A-2009-256589 may be used as appropriate. .

(2) Polyamidimide

The polyamidoximine used in the present invention is a polyamidoximine containing, as a structural unit, an acid component of a tricarboxylic acid or a tetracarboxylic acid, a dicarboxylic acid, and an amine component.

Among the polyamidoximines used, the acid components are:

a) tricarboxylic acid; diphenyl ether-3,3',4'-tricarboxylic acid, diphenylguanidin-3,3',4'-tricarboxylic acid, benzophenone-3,3',4' - an anhydride, an esterified product, or the like of a tricarboxylic acid such as a tricarboxylic acid, a naphthalene-1,2,4-tricarboxylic acid or a butane-1,2,4-tricarboxylic acid, or the like, or two or more thereof mixture.

b) tetracarboxylic acid; diphenyl hydrazine-3,3',4,4'-tetracarboxylic acid, naphthalene-2,3,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid Acid, naphthalene-1,4,5,8-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, cyclopentane-1,2,3,4-tetracarboxylic acid monohydrate, A dianhydride, an esterified product or the like, or a mixture of two or more thereof.

c) a dicarboxylic acid; adipic acid, sebacic acid, sebacic acid, a dicarboxylic acid of cyclohexane-4,4'-dicarboxylic acid, and one of these anhydrates or esters.

The amine composition is:

d) amine component

3,3'-Dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4 , 4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl , 3,3'-diethoxy-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 3,3'-diaminobenzimidamide, 4,4'-diaminobenzimidamide, 4,4'-diaminobenzophenone, 3,3'- Diaminobenzophenone, 3,4'-diaminobenzophenone, 2,6-methyl-tolyldiamine, 2,4-tolyldiamine, 4,4'-diaminodi Phenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 3,3'- Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, p-xylenediamine, m-xylenediamine, 2,2'-bis(4-aminophenyl)propane , 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxyl) Benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-amino) Phenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]propane, 4,4'- Bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, tetramethyldiamine, hexamethylenediamine, isophorone II An amine, 4,4'-dicyclohexylmethanediamine, cyclohexane-1,4-diamine, diamine oxirane, or a diisocyanate corresponding thereto, or a mixture of two or more thereof.

In particular, the acid component is trimellitic anhydride (TMA), 3,3,4',4'-benzophenonetetracarboxylic dianhydride (BTDA), and 3,3,4',4'- Biphenyltetracarboxylic dianhydride (BPDA), isocyanate composition 1,5- A raw material of naphthalene diisocyanate (NDI), which is obtained by polymerization, is preferably a polyamidoximine resin.

The molar ratio of the ruthenium imine bond of the polyamidoximine to the guanamine bond is preferably 99/1 to 60/40 molar ratio, more preferably 99/1 to 75/25, and particularly preferably 90/10~80/20. When the molar ratio of the quinone imine bond to the guanamine bond is 60/40 or more, heat resistance, moisture resistance, and heat resistance can be improved. Further, when it is 99/1 or less, the modulus of elasticity is lowered, and the flexural resistance and the bending property tend to be improved.

(2.1) Polyamidoquinone imine with the structure represented by formula (2) as an essential component

In a preferred embodiment, the molecular chain contains the structure represented by the formula (2) as an essential component, and has at least the group selected by the formulas (3), (4) and (5). One type of structure is used as a repeating unit of a polyamidoximine resin.

(X represents an oxygen atom, CO, SO ₂ , or a bond. n represents 0 or 1).

(Y represents an oxygen atom, CO, or OOC-R-COO. n represents 0 or 1, and R represents a divalent organic group).

Wherein, in the formula (3), X is SO ₂ or a bond (biphenyl bond), or n = 0 is preferred. More preferably, X is a bond (biphenyl bond), or n=0. In the formula (4), Y is preferably a benzophenone type (CO) or a bonded type (biphenyl bond).

In a preferred embodiment, the formula (2) is a repeating unit formed of trimellitic anhydride and 1,5-naphthalene diisocyanate, and the formula (3) is terephthalic acid and 1,5-naphthalene diisocyanate. The repeating unit formed, formula (4) is a repeating unit formed of biphenyltetracarboxylic dianhydride, or benzophenone tetracarboxylic dianhydride and 1,5-naphthalene diisocyanate, and the ratio thereof is Formula (2) / {Formula (3) + Formula (4) + Formula (5)} = 1 / 99 ~ 40 / 60 molar ratio, and, Equation (3) / Formula (4) = 10 / 90 ~ 90 /10 Mo Erbi is better.

The higher the niobium amination rate, the better, and the upper limit is 100%. The above polyamidoximine resin can be synthesized by a usual method. For example, an isocyanate method, an amine method (acid chloride method, low-temperature solution polymerization method, room temperature solution polymerization method, etc.), etc., and the polyamidoximine resin used in the present invention is preferably one which is soluble in an organic solvent, such as As described above, it is preferable to obtain it by the isocyanate method for the reason of ensuring the reliability of the peel strength (the strength). Further, it is industrially preferable because it can be applied by using a solution at the time of polymerization.

(2.2) Polyamidoquinone imine having the structure represented by formula (6) or formula (7)

As the preferred polyamidoximine resin, a compound containing the following formula (6) as a structural unit can be used. Hereinafter, a compound having a structure represented by the formula (6) will be described.

(wherein R ₁ is an aryl group or a cycloalkyl group, which may contain nitrogen, oxygen, sulfur, or halogen).

(Diamine component of polyamidoximine resin)

Further, a diamine component, for example, p-phenylenediamine, m-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 4,4' -diaminodiphenyl hydrazine, 3,3'-diaminodiphenyl hydrazine, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 3,3'-diamino Benzoquinone aniline, 4,4'-diaminobenzimidamide, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-di Aminobenzophenone, 2,6-methyl-tolyldiamine, 2,4-tolyldiamine, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodi Phenyl sulfide, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 3,3'-diaminodiphenylmethane, 4,4'-di Aminodiphenylmethane, P-xylylenediamine, m-xylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalene Diamine, 2,2'-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene , 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, bis[4-(4-aminophenoxy) Phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl碸, bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'- Bis(3-aminophenoxy)biphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4-methyl-1,3-phenylenediamine, 3,3 '-Diethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4' -diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-diethoxy-4,4'-diaminobiphenyl, anti Formula - 1,4-diaminocyclohexane, cis-1,4-diaminocyclohexane, 1,4-diaminocyclohexane (trans/cis mixture), 1,3- Diaminocyclohexane, dicyclohexylmethane-4,4'-diamine (trans, cis, trans/cis mixture), isophorone diamine, 1,4-cyclohexane Bis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 3,8-double (Aminomethyl)tricyclo[5.2.1.0]decane, 1,3-diamine adamantane, 4,4'-extended methylbis(2-methylcyclohexylamine), 4,4'-stretch Methyl bis(2-ethylcyclohexylamine), 4,4'-extended methyl bis(2,6-dimethylcyclohexylamine), 4,4'-extended methyl bis (2,6-di Ethylcyclohexylamine), 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexa Propane, 1,3-propanediamine, 1,4-extended tetramethyldiamine, 1,5-extended pentamethyldiamine, 1,6-extended hexamethyldiamine, 1,7-extension Alkali diamine, 1,8-extended octamethyldiamine, 1,9-extended hexamethyldiamine, or the like, or a mixture of two or more thereof, or corresponding to the diisocyanate or the like, Alternatively, two or more kinds of mixtures may be used as the diamine component.

Preferably, 3,3'-dimethyl-4,4'-diaminobiphenyl, dicyclohexylmethane-4,4'-diamine (trans, cis, trans/cis) a mixture), 4,4'-diaminodiphenyl ether, p-phenylenediamine, 4-methyl-1,3-phenylenediamine, or the like, or a mixture of two or more, or Separately, or a mixture of two or more of these diisocyanates may be used as The diamine component is used.

More preferably, 3,3'-dimethyl-4,4'-diaminobiphenyl, dicyclohexylmethane-4,4'-diamine (trans, cis, trans/cis a mixture), 4,4'-diaminodiphenyl ether, 4-methyl-1,3-phenylenediamine, or the like, or a mixture of two or more thereof, or corresponding to the diisocyanate or the like. Separately, or a mixture of two or more kinds may be used as the diamine component.

Particularly preferred, 3,3'-dimethyl-4,4'-diaminobiphenyl, dicyclohexylmethane-4,4'-diamine (trans, cis, trans/cis The mixture), 4-methyl-1,3-phenylene diamine, or the like, or a mixture of two or more thereof, or a mixture of two or more of the above-mentioned diisocyanates, or a mixture of two or more thereof may be used. Used as a diamine component.

(a combination of preferred acid components and diamine components)

Among the above-mentioned acid component and diamine component, heat resistance, solvent resistance, and durability in the film forming process, and heat resistance and surface smoothness of the obtained polyimide film, and From the viewpoints of transparency, etc., it is preferable to use the following components.

As the acid component, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride can be used. A polyamidoximine resin having a cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride as an acid component can be used.

As the diamine component, at least one selected from the group consisting of 3,3'-dimethyl-4,4'-diaminobiphenyl and 4-methyl-1,3-phenylenediamine can be used. Or two compounds, or from 3,3'-dimethyl-4,4'-diisocyanate biphenyl (o- At least one or two compounds selected from the group consisting of toluidine diisocyanate and 4-methyl-1,3-phenylene diisocyanate (tolyl diisocyanate).

Further, as the polyacrylamide imide resin, a compound having a structure represented by the following formula (7) as a structural unit can be used.

(wherein R ₂ and R ₃ each independently represent hydrogen, an alkyl group having 1 to 3 carbon atoms or an aryl group, and may contain nitrogen, oxygen, sulfur, or halogen).

Further, when the total acid component is 100 mol%, the acid component exemplified may contain 50 mol% or more and 100% or less, more preferably 70 mol% or more and 100% or less. Further, when the total diamine component is 100 mol%, the diamine component exemplified may contain 50 mol% or more and 100% or less, more preferably 70 mol% or more and 100% or less. In these ranges, it is particularly preferable in terms of heat resistance and durability in the film forming process, and heat resistance, surface smoothness, and transparency of the obtained polyimide film. .

The molecular weight of the polyamidoximine resin used is N-methyl-2-pyrrolidone (polymer concentration: 0.5 g/cm ³ ), and the logarithmic viscosity at 30 ° C is equivalent to 0.3 to A molecular weight of 2.5 cm ³ /g is preferred, and a molecular weight equivalent to 0.5 to 2.0 cm ³ /g is more preferred. When the logarithmic viscosity is 0.3 cm ³ /g or more, mechanical properties can be sufficiently obtained when a molded article such as a film is formed. Moreover, when it is 2.0 cm ³ /g or less, since the viscosity of the solution is not too high, it is easy to carry out a molding process.

(3) polyether quinone

The polyether oximine used in the present invention. The thermoplastic resin having an aromatic nucleus bond and a quinone imine bond in its structural unit is not particularly limited, and specifically, it has a formula (8) or a formula (9) below. The repeating unit of the structure is preferably a polyether oximine.

The polyether sulfimine having a repeating unit of the structure represented by the above formula (8), for example, the trade name "Ultem" manufactured by Singular Electronics Co., Ltd. "1000" (glass transition temperature: 216 ° C), "Ultem 1010" (glass transition temperature: 216 ° C), a polyether sulfimine having a repeating unit of the structure represented by the above formula (9), for example, "Ultem For example, the product name "AURUM PL500AM" (glass transition temperature: 258 ° C) manufactured by Mitsui Chemicals Co., Ltd., and the like are exemplified by CRS5001 (glass transition temperature: Tg 226 ° C).

The method for producing the polyether sulfimine is not particularly limited, and usually, the amorphous polyether quinone having the structure represented by the above formula (8), for example, 4, 4'-[ a condensed polymer of propylbis(p-phenylene oxide)dicarboxylic acid dianhydride and m-phenylenediamine, or a polyetherimine having the structure represented by the above structural formula (9), A condensed polymer of 4,4'-[isopropylidene bis(p-phenylene)]dicarboxylic dianhydride and p-phenylenediamine was synthesized by a known method.

Further, the polyether oximine may contain other monomer units which can form a copolymerization such as a mercapto group, an ester group or a sulfonyl group, without exceeding the scope of the present invention. Further, the polyether phthalimide may be used alone or in combination of two or more.

(4) Polyester quinone

The resin having the quinone imine structure used in the present invention preferably contains a polyester quinone imine structure represented by the formula (10) in a structural unit.

(In the formula (10), R ₁ represents a divalent group having a specific structure. R ₂ represents a divalent chain aliphatic group, a divalent cyclic aliphatic group or a divalent aromatic group).

In the formula (10), R ₁ represents a divalent group having a structure represented by the formula (11), the formula (12) or the formula (13), respectively.

(a divalent base having the structure represented by the formula (11))

In the formula (11), R represents a divalent chain aliphatic group, a cyclic aliphatic group or an aromatic group, and a plurality of R may be the same or different from each other. These chain aliphatic groups, cyclic aliphatic groups or aromatic groups may be used singly or in combination of two or more kinds.

When m is a positive integer of 1 or more, it is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. Also, the upper limit of m is not special. The limit is preferably 25 or less, more preferably 20 or less, still more preferably 10 or less. When it exceeds 25, heat resistance tends to decrease.

The chain aliphatic group, cyclic aliphatic group or aromatic group is represented by "chain aliphatic compound having a divalent hydroxyl group", "cyclic aliphatic compound having a divalent hydroxyl group" or "having a divalent hydroxyl group" The residue derived from a diol such as an aromatic compound is preferred. Further, it may be a residue derived from a "polycarbonate diol" obtained by polymerizing a diol, a carbonate, or phosgene.

The "chain aliphatic compound having a divalent hydroxyl group" may be a branched or branched diol having two hydroxyl groups. For example, alkylene glycol, polyoxyalkylene glycol, polyester diol, polycaprolactone diol, and the like. A branched or linear diol having two hydroxyl groups which can be used as a "chain aliphatic compound having a divalent hydroxyl group", for example, is as follows.

Alkanediol, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl Base-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10 - decanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like.

a polyoxyalkylene glycol, for example, dimethylolpropionic acid (2,2-bis(hydroxymethyl)propionic acid), dimethylolbutanoic acid (2,2-bis(hydroxymethyl)butanoic acid), Polyethylene glycol, polypropylene glycol, polytetramethyl glycol, polyoxytetramethyl glycol, random copolymer of tetramethyl glycol and neopentyl glycol. Preferred is polyoxytetramethyl diol.

a polyester diol, for example, a polyol exemplified below A polyester diol or the like obtained by reacting a polybasic acid.

As the "polyol component" used in the polyester diol, any of various polyols can be used. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol can be used. 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-tri Methyl-1,3-pentanediol, cyclohexanemethanol, neopentylhydroxytrimethylacetate, ethylene oxide adduct of bisphenol A, propylene oxide adduct, hydrogenated bisphenol A Ethylene oxide adduct and propylene oxide adduct, 1,9-nonanediol, 2-methyloctanediol, 1,10-dodecanediol, 2-butyl-2-ethyl A polyether polyol such as 1,3-propanediol, tricyclodecane methanol, polyethylene glycol, polypropylene glycol or polytetramethyl glycol.

As the "polybasic acid component" used in the polyester diol, any of various polybasic acids can be used. For example, terephthalic acid, isophthalic acid, isophthalic acid, 1,5-naphthoic acid, 2,6-naphthoic acid, 4,4'-diphenyldicarboxylic acid, 2,2'- can be used. Diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, adipic acid, sebacic acid, sebacic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexane An aliphatic or alicyclic dibasic acid such as a carboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohexanedicarboxylic acid or a dimer acid.

A commercial product of a polyester diol, specifically, for example, ODX-688 (DIC aliphatic polyester diol: adipic acid/neopentyl glycol/1,6-hexanediol, number average) The molecular weight is about 2,000), Vylon (registered trademark) 220 (polyester diol manufactured by Toyobo Co., Ltd., number average molecular weight: about 2,000).

Polycaprolactone diol, for example, γ-butyl lactone, ε-hexene A polycaprolactone diol obtained by a ring-opening addition reaction of a lactone such as an ester or δ-valerolactone.

The above-mentioned "chain-type aliphatic compound having a divalent hydroxyl group" may be used singly or in combination of two or more kinds.

"A cyclic aliphatic compound having a divalent hydroxy group" or "an aromatic compound having a divalent hydroxy group", "a compound having two hydroxyl groups on an aromatic ring or a cyclohexane ring", "two phenols or an alicyclic ring" may be used. A compound obtained by bonding a divalent functional group with a divalent functional group, a compound having a hydroxyl group on each of two cores of a biphenyl structure, and a compound having two hydroxyl groups on a naphthalene skeleton.

"Aromatic ring or a compound having two hydroxyl groups on a cyclohexane ring", hydroquinone, 2-methylhydroquinone, resorcinol, catechol, 2-phenylhydroquinone, cyclohexanedimethanol can be used. , tricyclodecane methanol, 1,4-dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,2-dihydroxycyclohexane, 1,3-adamantanediol, dicyclopentane Alkene 2 water and 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoin A carboxyl group-containing diol such as an acid or a 3,5-dihydroxybenzoic acid.

"2 phenols", or "alicyclic alcohols are compounds obtained by bonding a divalent functional group", for example, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy group can be used. Benzoquinone, 4,4'-(9-fluorenylidene) diphenol, 4,4'-dihydroxydicyclohexyl ether, 4,4'-dihydroxydicyclohexanide, bisphenol A, double Phenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like.

Also, "the biphenyl structure has one hydroxy group on each of the two cores. For example, 4,4'-bisphenol, 3,4'-bisphenol, 2,2'-bisphenol, 3,3',5,5'-tetramethyl-4,4 can be used. '-bisphenol, etc.

As an example of the "compound having two hydroxyl groups on the naphthalene skeleton", 2,6-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,8-naphthalenediol or the like can be used.

The number average molecular weight of the diol is preferably 100 or more and 30,000 or less, more preferably 150 or more and 20,000 or less, and particularly preferably 200 or more and 10,000 or less. When the number average molecular weight is less than 100, the low hygroscopicity and flexibility cannot be sufficiently exhibited.

When the content is higher than 30,000, the composition and structure of the "diol" are affected by the composition and structure of the diamine component (or isocyanate component) described later, and phase separation occurs, and mechanical properties cannot be fully exerted. Characteristics, colorless transparency.

The polycarbonate diol may be a polycarbonate diol (copolycarbonate diol) having the above-mentioned plurality of alkylene groups in the skeleton. For example, a combination of 2-methyl-1,8-octanediol and 1,9-nonanediol, a combination of 3-methyl-1,5-pentanediol and 1,6-hexanediol, 1, A copolymerized polycarbonate diol obtained by synthesizing a combination of 5-pentanediol and 1,6-hexanediol. Preferred is a copolymerized polycarbonate diol obtained by synthesizing a combination of 2-methyl-1,8-octanediol and 1,9-nonanediol. These polycarbonate diols can be used in combination of two or more kinds.

Commercial products of the polycarbonate diol which can be used include, for example, KURAREPOLYOL C series manufactured by KURARE, and DURNOL series manufactured by Asahi Kasei Chemicals Co., Ltd. For example, KURAREPOLYOL C-1015N, KURAREPOLYOL C-1065N ((share) KURARE production of carbonic acid Ester diol: 2-methyl-1,8-octanediol/1,9-nonanediol, number average molecular weight about 1000), KURAREPOLYOL C-2015N, KURAREPOLYOL C2065N (() KURARE carbonate diol: 2-methyl-1,8-octanediol/1,9-nonanediol, number average molecular weight about 2000), KURAREPOLYOL C-1050, KURAREPOLYOL C-1090 (() KURARE carbonate diol: 3- Methyl-1,5-pentanediol/1,6-hexanediol, number average molecular weight about 1000), KURAREPOLYOL C-2050, KURAREPOLYOL C-2090 (() KURARE carbonate diol: 3-methyl -1,5-pentanediol/1,6-hexanediol, number average molecular weight about 2000), DURNOL T5650E (asahi Kasei Chemicals Co., Ltd. polycarbonate diol: 1,5-pentanediol/1,6 - hexanediol, number average molecular weight about 500), DURNOL T5651 (polycarbonate diol manufactured by Asahi Kasei Chemical Co., Ltd.: 1,5-pentanediol / 1,6-hexanediol, number average molecular weight of about 1000), DURNOL T5652 (polycarbonate diol manufactured by Asahi Kasei Chemical Co., Ltd.: 1,5-pentanediol/1,6-hexanediol, number average molecular weight: about 2,000). It is preferably KURAREPOLYOL C-1015N or the like.

The method for producing the polycarbonate diol includes, for example, transesterification of a raw material diol with a carbonate, reaction of a raw material diol with phosgene dehydrogenation, and the like. The carbonate as a raw material is, for example, a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate; a diaryl carbonate such as diphenyl carbonate; and an ethylene carbonate or propylene carbonate. Alkyl carbonate.

(a divalent base having the structure represented by the formula (12))

A divalent group having the structure represented by the formula (12) will be described.

In the formula (12), R ₃ represents a linear chain, an alkylene group (-C _n H _2n -), a perfluoroalkylene group (-C _n F _2n -), an ether bond (-O-), an ester bond. (-COO-), carbonyl (-CO-), sulfonyl (-S(=O) ₂ -), sulfinyl (-SO-), fluorenylene (-S-), carbonic acid Root (-OCOO-), or fluorenylidene. n is a positive integer of 1 or more. The upper limit of n is not particularly limited, but is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. X ₁ to X ₈ may be the same or different, and each represents hydrogen, halogen or alkyl.

Specific examples of the divalent group having the structure represented by the formula (12) are, for example, but not particularly limited, and may be a diphenyl ether skeleton, a diphenylfluorene skeleton, or a 9-fluorenylidene diphenol. The skeleton, the bisphenol A skeleton, the bisphenol F skeleton, the ethylene oxide adduct skeleton of bisphenol A, the propylene oxide adduct skeleton of bisphenol A, the biphenyl skeleton, the naphthalene skeleton, and the like.

The above skeleton is preferably a residue derived from a compound having one hydroxyl group on each of two benzene rings of the formula (12). As the raw material of the divalent group having the structure represented by the formula (12), 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl hydrazine, 4,4'-(9-Asia) can be used. Dimethyl phenol, bisphenol A, bisphenol F, ethylene oxide adduct of bisphenol A, propylene oxide addition of bisphenol A , 4,4'-bisphenol, 3,4'-bisphenol, 2,2'-bisphenol, 3,3',5,5'-tetramethyl-4,4'-bisphenol, 2, 6-naphthalenediol, 1,4-naphthalenediol, 1,5-naphthalenediol or 1,8-naphthalenediol.

Preferred is ethylene oxide addition of 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl hydrazine, 4,4'-(9-fluorenylene) diol or bisphenol A. Things. Particularly preferred is an ethylene oxide adduct of 4,4'-dihydroxydiphenyl ether or bisphenol A.

These compounds may be used alone or in combination of two or more. When these raw materials are used, the above-mentioned diphenyl ether skeleton or the like can be introduced at the R ₁ position of the formula (10).

(a divalent base having the structure represented by the formula (13))

In the formula (13), R ₄ represents a linear chain, an alkylene group (-C _n H _2n -), a perfluoroalkylene group (-C _n F _2n -), an ether bond (-O-), an ester bond. (-COO-), carbonyl (-CO-), sulfonyl (-S(=O) ₂ -), sulfinyl (-SO-), fluorenylene (-S-), carbonic acid Root (-OCOO-), or fluorenylidene. n is a positive integer of 1 or more. The upper limit of n is not particularly limited, but is preferably 10 or less, more preferably 5 or less, still more preferably 3 or less. X ₁ '~X ₈ ' may be the same or different, and each represents hydrogen, halogen or alkyl.

Specific examples of the divalent group having the structure represented by the formula (13) are, for example, but not particularly limited, and may be a dicyclohexyl ether skeleton, a bicyclohexyl skeleton, a hydrogenated bisphenol A skeleton, or a hydrogenation double A phenol F skeleton, an ethylene oxide adduct skeleton of hydrogenated bisphenol A, or a propylene oxide adduct skeleton of hydrogenated bisphenol A.

The above skeleton is preferably a residue derived from a compound having one hydroxyl group in each of two cyclohexane rings of the formula (13). As the raw material of the divalent group having the structure represented by the formula (13), 4,4'-dihydroxydicyclohexyl ether, 4,4'-dihydroxydicyclohexanide, hydrogenated bisphenol A, hydrogenation double can be used. Phenol F, an ethylene oxide adduct of hydrogenated bisphenol A, or a propylene oxide adduct of hydrogenated bisphenol A, and the like.

Preferred is 4,4'-dihydroxydicyclohexyl ether or 4,4'-dihydroxydicyclohexanide.

These compounds may be used alone or in combination of two or more. When these raw materials are used, the above-mentioned dicyclohexyl ether skeleton or the like can be introduced at the R ₁ position of the formula (10).

When the structure of the formula (10) is exemplified, a halide of cyclohexanetricarboxylic anhydride can be reacted with a diol to obtain a tetracarboxylic dianhydride containing an ester group, and secondly, the ester will be contained. The tetracarboxylic dianhydride can be obtained by a condensation reaction (polyimidization) with a diamine or a diisocyanate.

(having a divalent base of the structure represented by the formula (14))

Polyester quinone imine resin, which can contain the formula (14) in the structural unit The structure of the show.

R ₂ of the formula (10) and R ₂ ' of the formula (14) will be described. R ₂ and R ₂ ' are not particularly limited as long as they independently represent a divalent chain aliphatic group, a divalent cyclic aliphatic group or a divalent aromatic group. The "two-valent chain aliphatic group", the "two-valent cyclic aliphatic group", and the "two-valent aromatic group" may be used alone or in combination of two or more.

R ₂ is a divalent group having a structure represented by the following formula (15), and R ₂ ' is a divalent group having a structure represented by the following formula (16).

(having a divalent base of the structure represented by the formula (15))

R ₂ in the above formula (10) is preferably a divalent group having a structure represented by the formula (15) in terms of a balance of heat resistance, flexibility, and low hygroscopicity.

In the formula (15), R ₅ represents a linear chain, an alkylene group (-C _n H _2n -), a perfluoroalkylene group (-C _n F _2n -), an ether bond (-O-), an ester bond. (-COO-), carbonyl (-CO-), sulfonyl (-S(=O) ₂ -), sulfinyl (-SO-) or fluorenylene (-S-). n is preferably a positive integer of 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. X ₉ to X ₁₆ may be the same or different, and each represents hydrogen, halogen or alkyl.

(having a divalent base of the structure represented by the formula (16))

R ₂ ' in the above formula (14) is preferably a divalent group having a structure represented by the formula (16) in terms of a balance of heat resistance, flexibility, and low hygroscopicity.

In the formula (16), R ₅ ' represents a linear chain, an alkylene group (-C _n H _2n -), a perfluoroalkylene group (-C _n F _2n -), an ether bond (-O-), an ester bond. A knot (-COO-), a carbonyl group (-CO-), a sulfonyl group (-S(=O) ₂ -), a sulfinyl group (-SO-) or an anthranylene group (-S-). n is preferably a positive integer of 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or more and 3 or less. X ₉ '~X ₁₆ ' may be the same or different, and each represents hydrogen, halogen or alkyl.

In the formulas (10) and (14), the "two-valent chain aliphatic group", the "two-valent cyclic aliphatic group" or the "two-valent aromatic group" are introduced into the formula (10). _{In the case of the 2} position and the R ₂ ' position of the formula (14), it is preferred to use the corresponding diamine component or diisocyanate component, respectively. In other words, the "aromatic diamine or the corresponding aromatic diisocyanate", the "cyclic aliphatic diamine or the corresponding cyclic aliphatic diisocyanate", or the "chain aliphatic diamine" or the corresponding In the case of a chain aliphatic diisocyanate, a polyester quinone imine resin having excellent heat resistance, flexibility, and low hygroscopicity can be obtained.

The diamine component of R _{2 of the} formula (10) and the R ₂ ' of the formula (14) or the diisocyanate component corresponding thereto may be the same or different. In the case of a preferred manufacturing method to be described later, the same is preferred.

The diamine component using R ₂ and R ₂ ' as a basic skeleton or a diisocyanate component corresponding thereto will be described.

"Aromatic diamine or an aromatic diisocyanate corresponding thereto", specifically, when a diamine compound is exemplified, for example, 2,2'-bis(trifluoromethyl)benzidine, p-phenylenediamine , m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, 2,4-diaminopurine (durene), 4, 4'-Diaminodiphenylmethane, 4,4'-methyl bis(2-methylaniline), 4,4'-methyl bis(2-ethylaniline), 4,4'- Methyl double (2,6-dimethylaniline), 4,4'-extended methyl bis(2,6-diethylaniline), 4,4'-diaminodiphenyl ether, 3,4'-diamine Diphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl hydrazine, 3,3'-diamino group Benzoquinone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfide, 3,3'-diamine Diphenyl sulfide, 4,4'-diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminobenzimidil, P-xylene Diamine, m-xylylenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, benzidine, 3,3'- Dihydroxybenzidine, 3,3'-dimethoxybenzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4' -diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3 '-Dimethoxy-4,4'-diaminobiphenyl, 3,3'-diethoxy-4,4'-diaminobiphenyl, o-toluidine, m-toluidine, 1 , 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-double ( 3-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)phenyl)anthracene, bis(4- (4-Aminophenoxy)phenyl)indole, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 2,2-bis(4-(4-aminobenzene) Oxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, diamine-linked triphenyl, and the like. Further, these may be used in combination of two or more kinds.

Further, the "cyclic aliphatic diamine or the cyclic aliphatic diisocyanate corresponding thereto" is exemplified by a diamine compound, for example, trans-1,4-diaminocyclohexane, cis-1, 4-diaminocyclohexane, 1,4-diaminocyclohexane (trans/cis mixture), 1,3-diaminocyclohexane, 4,4'-extended methyl double (ring Hexylamine) (trans, cis, trans/cis mixtures), Isophoronediamine, 1,4-cyclohexanebis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminemethyl) Bicyclo [2.2.1] heptane, 3,8-bis(aminomethyl)tricyclo[5.2.1.0]nonane, 1,3-diamine adamantane, 4,4'-extended methyl double (2 -Methylcyclohexylamine), 4,4'-methyl bis(2-ethylcyclohexylamine), 4,4'-methyl bis(2,6-dimethylcyclohexylamine), 4 , 4'-Extended methyl bis(2,6-diethylcyclohexylamine), 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexa Fluoropropane, etc. Further, these may be used in combination of two or more kinds.

The "chain aliphatic diamine or the chain aliphatic diisocyanate corresponding thereto" is exemplified by a diamine compound, for example, 1,3-propanediamine, 1,4-tetramethyldiamine, 1, 5-extended pentamethyldiamine, 1,6-exeting hexamethyldiamine, 1,7-exeting heptamethyldiamine, 1,8-extended octamethyldiamine, 1,9-extension Diamine and the like. Further, these may be used in combination of two or more kinds.

Of heat resistance, flexibility, low moisture absorption of the balance point of view, the formula (10) and R ₂ in the formula (14) in the R ₂ 'corresponding to the diamine component or the diisocyanate component in the preferred The composition, when exemplified by a diamine compound, is, for example, p-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, 4,4'-diamino group Residues derived from diphenyl ether, 1,5-naphthalenediamine, o-toluidine, diaminotriphenyl, 4,4'-methyl bis(cyclohexylamine), isophorone diamine, etc. base. More preferably from 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 1,5-naphthalenediamine, o-toluidine, particularly preferably 4,4' -diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, o-toluidine, preferably derived from 4,4'-diaminodiphenylmethane, o-toluidine Residues.

Since the polymethyleneamine of the present invention contains fluorinated polyamidamine, it is preferable from the viewpoint of having excellent transparency of the polyimide film and heat correction by heat shrinkage. When the content of fluorine is in the range of 1 to 40% by mass in the film, the effect of the present invention can be improved.

<Physical properties of polyamidamine film> (full light penetration rate)

The polyimine film of the present invention is preferably a transparent polyimide film. In terms of transparency, when the sample having a thickness of 55 μm is obtained, the total light transmittance is preferably 80% or more. More than 85% is preferred, and more preferably 90% or more. The higher the total light transmittance, the higher the transparency, and the better. The value of the total light transmittance of 80% or more is described as a preferred range.

The total light transmittance of the polyimide film was measured in an air-conditioned room at ‧55% RH at 23 ° C, and a sample of a polyimide film which was conditioned for 24 hours was measured in accordance with JIS K 7375-2008. The measurement was performed using a spectrophotometer U-3300 of Hitachi High-Tech Co., Ltd., and the transmittance in the visible light region (range of 400 to 700 nm) was measured.

The type of polyamine can be selected to adjust the total light transmittance to 80% or more.

(yellow index value (YI value))

The polyamidamine film of the invention is a colorless polyamidamine film good. The colorless standard is that the yellow index value (YI value) is preferably 4.0 or less, more preferably 0.3 to 2.0, and particularly preferably 0.3 to 1.6. The smaller the yellow index value (YI value), the smaller the coloring, and the better. The yellow index value (YI value) is a numerical value of 4.0 or less, and is a preferred range.

The value of the aforementioned YI value can be adjusted by selecting the type of the above polyamine.

The yellow index value is obtained by the YI (yellow index: coefficient of yellowness) of the film specified in JIS K 7103.

The method for measuring the yellow index value is to prepare a sample of the film, and then use the Hitachi Hi-Tech spectrophotometer U-3300 and the attached chroma calculation program to obtain the third color of the light source specified in JIS Z 8701. The stimulus values X, Y, and Z are obtained, and the yellow index value is obtained according to the definition of the following formula.

Yellow index value (YI value) = 100 (1.28X-1.06Z) / Y

(solubility)

The polyamidene of the present invention has a critical amount (solubility) of 100 g of dimethylacetamide or 100 g of γ-butyrolactone dissolved at 60 ° C of 1 g or more. Therefore, the solubility of either 100 g of dimethylacetamide or 100 g of γ-butyrolactone may be 1 g or more. When the solubility is 1 g or more, it can be easily produced by a solution extension method. When the solubility is larger, it is more preferably produced by a solution extension method. The numerical value of the solubility of 1 g or more is a standard which shows the preferable range of soluble polyimine.

The solubility of the polymethyleneamine of the present invention can be adjusted in such a manner that the type of the polyimide used in the present invention can be selected.

In order to make the polyimine soluble, it is generally effective to reduce the ratio of the structure of the quinone imine group and the aromatic hydrocarbon which can act to improve the planarity of the molecular skeleton of the polyamidamine. Further, it is also effective to introduce a structural isomer, a bent group, or introduce an aliphatic group or an alicyclic group into an aromatic group, and introduce a fluorine atom or a skeleton having a high bulk density.

a compound, for example, an alicyclic, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4, 5-cyclohexanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, (bicyclo[4.2.0] Octane-3,4,7,8-tetracarboxylic dianhydride)bicyclo[2.2.1]heptanedimethaneamine, a structure having a flexural group, for example, 2,3',3,4'-linked Pyromellitic dianhydride, 3,4'-oxophthalic anhydride, 4,4' oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylic acid Anhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)malonate, bis[4 -(4-Aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis(3-aminophenyl)anthracene, 3,3' - Diaminobenzophenone, 3,4'-diaminodiphenyl ether, and the like.

Further, a compound containing a fluorine atom, for example, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,2'-bis(trifluoromethyl)benzidine, 2,2-dual ( 3-Amino-4-hydroxyphenyl)hexafluoropropane, a compound containing a mercapto group, for example, 9,9-bis(4-amino-3-fluorophenyl)anthracene, 9,9-bis[4- (3,4-dicarboxybenzene Oxy)-phenyl]indole anhydrate, 9,9-bis[4-(3,4-dicarboxyphenoxy)-phenyl]indole anhydrate, 9,9-bis(3,4-dicarboxyl Phenyl) phthalic anhydride or the like.

(turbidity value)

In the present invention, the polyiminamide film of the drum body after the heat treatment has a haze value of 4% or less, and it is more preferable from the viewpoint of improving the transparency of the polyimide film.

For the measurement of the turbidity, the turbidity (full turbidity) was measured using a turbidity meter NDH-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K 7136. When measured under the conditions of 23 ° C and ‧55% RH, the light source of the turbidity meter is a halogen ball using 5V9W, and the light receiving unit is a light-emitting battery (with a specific sensitivity filter).

(deviation of the turbidity value in the direction of the surface (standard deviation))

In the present invention, in the polyimide film of the drum body after the heat treatment, the variation in the surface direction of the haze value is small, and the standard deviation is 1 or less. More preferably 0.6 or less.

The standard deviation (σ) is the square root of the dispersion σ ² with respect to the average value of the measured values.

The average value can be calculated by the following formula (where x _i is each measured value, and n is the number of measurement points).

The dispersion σ ² can be calculated by the following formula.

The standard deviation of the surface direction of the turbidity value was measured using a polyimide film having a drum body of 1000 to 1900 mm width. The turbidity value was measured in the width direction of the drum body at intervals of 100 mm and 5 points. The measurement was carried out on three drum bodies, and the total turbidity was measured at 150 to 285 points.

The standard deviation of the turbidity values of 150 to 285 points was calculated as the deviation (standard deviation) of the turbidity value in the plane direction.

<Inorganic microparticles>

In the polyamidamine film of the present invention, inorganic fine particles are mixed.

When the mixing ratio of the inorganic fine particles in the polyimide film is 0.01% by mass or more, the smoothness can be improved. Therefore, the planarity of the long-twisted polyimide film is not easily deteriorated. Moreover, when it is 2.0% by mass or less, it has an effect of preventing an increase in the turbidity of the polyimide film.

As the inorganic fine particles, fine particles using the following inorganic compound are preferred. Examples of fine particles of inorganic compounds, for example, ceria, titania, alumina, zirconia, calcium carbonate, talc, clay, calcined kaolin, calcined calcium citrate, water and calcium citrate, aluminum citrate, citric acid Magnesium and calcium phosphate. When ruthenium is contained in the fine particles, it is preferable from the viewpoint of lowering the turbidity, and particularly preferably ruthenium dioxide.

The average particle diameter of the primary particles of the fine particles is preferably in the range of 5 to 400 nm, more preferably in the range of 10 to 300 nm. It is preferable that the particles contain a secondary aggregate in a range of 0.05 to 0.3 μm in the main particle diameter, and if the particles have an average particle diameter of 80 to 400 nm, aggregation is not required, and the primary particles are preferably contained. .

The smaller the average particle diameter of the primary particles of the inorganic fine particles, the better the difference in the haze value in the surface direction of the effect of the present invention is. The average particle diameter of the primary particles is preferably 30 nm or less, and more preferably 10 nm or less.

Further, when the inorganic fine particles are surface-modified to make the surface more hydrophobic, the difference in the haze value in the surface direction of the effect of the present invention is preferably low.

In the hydrophobic treatment of the inorganic fine particles, the surface modifying agent may, for example, be methyl(trimethoxy)decane, ethyl(trimethoxy)decane, hexyl(trimethoxy)decane or decyl(trimethoxy)decane. , vinyl (trimethoxy) decane, 2-[(3,4)-epoxycyclohexyl]ethyl (trimethoxy)decane, 3-glycidoxypropyl (trimethoxy)decane, 3 -Methyl propylene oxiranyl (trimethoxy) decane, 3-propenyl methoxypropyl (trimethoxy) fluorene Alkane, dimethyl decyl, alkyl decane, trimethyl decyl, silicone oil, dodecyl benzene sulfonic acid, and the like.

For example, those having an epoxy group include, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyl(dimethoxy)methylnonane, and 3 - Illustrative examples of glycidoxypropyltrimethoxydecane, diethoxy(3-glycidoxypropyl)methyldecane, and the like.

Further, the decane coupling agent having an amine group may, for example, be 3-(2-aminoethylamino)propyldimethoxymethylnonane or 3-(2-aminoethylamino)propyltrimethoxy. Decane, 3-(2-aminoethylamino)propyltriethoxydecane, 3-(3-aminopropylamino)propyltriethoxydecane, 3-(3-aminopropylamino)propane Trimethoxy decane, 3-aminopropyl diethoxymethyl decane, 3-aminopropyl triethoxy decane, 3-aminopropyl trimethoxy decane, and the like.

The trifunctional alkoxydecane may, for example, be 2-[(3,4)-epoxycyclohexyl]ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-ring Oxypropoxypropyltriethoxydecane, etc., these may be used alone or in combination of two or more.

The trifunctional alkoxydecane can be synthesized by a known method. Further, as a commercially available product, "KBM-303" (manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropane, 2-[(3,4)-epoxycyclohexyl]ethyltrimethoxydecane can be used. "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.) of triethoxy decane.

A surface treating agent having an amine group, for example, aminopropyltrimethoxydecane, aminopropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Base decane, N-2-(aminoethyl)-3-aminopropyl three Methoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-(2-aminoethylamino)propyldimethoxymethylnonane, 3- (2-Aminoethylamino)propyltrimethoxydecane, 3-(2-aminoethylamino)propyltriethoxydecane, 3-(3-aminopropylamino)propyltriethoxy Baseline, 3-(3-aminopropylamino)propyltrimethoxydecane, 3-aminopropyldiethoxymethyldecane, 3-aminopropyltriethoxydecane, 3-aminopropyl Trimethoxy decane O-phospholethanolamine, fluorine-containing alkoxy decane, for example, triethoxyfluorodecane, triethoxytrifluoromethylnonane, 1,1,2,2-tetrahydrogen Perfluorohexyltriethoxydecane, triethoxy-3,3,4,4,5,5,6,6,6-nonafluorohexyldecane, triethoxy[4-(trifluoromethyl) Phenyl]decane, and triethoxy (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) ) decane, etc.

The content of the fine particles in the polyimide film is preferably in the range of 0.01 to 1% by mass, particularly preferably in the range of 0.05 to 0.5% by mass.

When a polythene film having a multilayer structure is formed by a co-precipitation method, it is preferred that the surface contains the above-mentioned added amount of fine particles.

As the cerium oxide microparticles, for example, AEROSIL R972, R972V, R974, R812, 200, 200V, 300, R202, OX50, TT600 (the above is manufactured by Japan AEROSIL Co., Ltd.) can be used as a commercial product.

For the zirconia fine particles, for example, AEROSIL R976 and R811 (manufactured by Japan AEROSIL Co., Ltd.) can be used as market names.

Examples of resin fine particles, for example, polyoxyn resin, fluorine tree Grease and acrylic resin. Further, a polyoxyxylene resin is preferable, and those having a three-dimensional network structure are preferable, and for example, TOSPEARL 103, the same 105, the same 108, the same 120, the same 145, the same 3120, and the same 240 (above MOMENTIVE) The trade name is sold to the market.

Among them, AEROSIL 200V and AEROSIL R972V make it possible to keep the polyimide film low turbidity and have a larger effect of lowering the friction coefficient.

<Other additives> (UV absorber)

The polyamidamine film of the present invention is preferred because it contains an ultraviolet absorber and can improve light resistance. The ultraviolet absorber is intended to absorb ultraviolet rays of 400 nm or less and to improve light resistance, and particularly preferably has a transmittance of 370 nm at a wavelength of from 0.001 to 30%, more preferably from 1 to 20%, more preferably. Good is 2~10% range.

The ultraviolet absorber preferably used in the present invention may, for example, be a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, or the like. It is a UV absorber, particularly preferably a benzotriazole-based UV absorber and a benzophenone-based UV absorber.

For example, 5-chloro-2-(3,5-di-sec-butyl-2-hydroxyphenyl)-2H-benzotriazole, (2-2H-benzotriazol-2-yl)-6 - (dual chain and side chain dodecyl)-4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc., for example, Preferably, Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin of Tinuvin 928, etc., any of which is commercially available from BASF Japan. Among them, those who do not have a halogen are preferred.

In addition, with 1,3,5-three A discotic compound such as a cyclic compound is also suitable as an ultraviolet absorber.

The polyimine film of the present invention preferably contains two or more kinds of ultraviolet absorbers.

Further, as the ultraviolet absorber, a polymer ultraviolet absorber may be used, and in particular, a polymer absorber of the type described in JP-A-6-148430 is preferably used. Further, the ultraviolet absorber is preferably one which does not have a halogen.

The ultraviolet absorber may be dissolved in an alcohol such as methanol, ethanol or butanol, or an organic solvent such as dichloromethane, methyl acetate, acetone or dioxane or a mixed solvent thereof. It may be added to the dopant or added directly to the content of the dopant composition.

The amount of the ultraviolet absorber used cannot be generalized depending on the type of the ultraviolet absorber, the use conditions, etc., and generally, when the dry film thickness of the polyimide film is 15 to 50 μm, 0.5 to 10 with respect to the polyimide film. The range of % by mass is preferably in the range of 0.6 to 4% by mass.

(Antioxidants)

Antioxidants are also known as anti-deterioration agents. When the electronic device or the like is placed in a state of high humidity and high temperature, the polyimide film may be deteriorated.

Antioxidants, for example, can delay retardation in polyamido films The decomposition of the polyimide film caused by the residual amount of the solvent or the phosphoric acid of the phosphoric acid-based plasticizer has a function of preventing oxidation. Therefore, it is preferred that the polyimide film of the present invention contains an antioxidant.

As the antioxidant, the compound described in Paragraph No. 0108 to 0119 of JP-A-2010-271619 can be used.

The amount of the compound to be added is preferably in the range of 1 ppm to 1.0%, more preferably in the range of 10 to 1000 ppm, based on the polyimide film.

(phase difference control agent)

A phase difference controlling agent, a liquid crystal layer forming an alignment film, and a phase difference between the polarizing plate protective film and the liquid crystal layer can be added to the polyimide film to improve the display quality of the image display device such as a liquid crystal display device. It can be combined with other methods to impart optical compensation to the polyimide film.

The phase difference controlling agent is, for example, an aromatic compound having two or more aromatic rings described in the specification of the European Patent No. 911656A2, and a rod-shaped compound described in JP-A-2006-2025. Further, it may be used in combination with two or more kinds of aromatic compounds. Among the aromatic rings of the aromatic compounds, in addition to the aromatic hydrocarbon ring, an aromatic heterocyclic ring containing an aromatic heterocyclic ring is preferred. An aromatic heterocyclic ring is generally an unsaturated heterocyclic ring. Among them, the 1,3,5-three described in the special publication No. 2006-2026 The ring is better.

The amount of phase difference control agent added is relative to poly The guanamine film-based resin is preferably 100% by mass, preferably 0.5 to 20% by mass, and preferably 1 to 10% by mass.

(peeling accelerator)

In the polyimine film of the present invention, a peeling accelerator can be added from the viewpoint of improving the peeling property at the time of film production.

Among the additives which can reduce the peeling resistance of the polyimide film, there are many significant effects in the surfactant. Preferred examples of the release agent include a phosphate ester surfactant, a carboxylic acid or a carboxylate. A surfactant, a sulfonic acid or sulfonate surfactant, and a sulfate surfactant are effective. Further, a fluorine-based surfactant in which a part of hydrogen atoms to which a hydrocarbon chain of the surfactant is bonded is replaced by a fluorine atom is also effective. The following is an illustration of the stripper.

RZ-1 C ₈ H ₁₇ OP(=O)-(OH) ₂

RZ-2 C ₁₂ H ₂₅ OP(=O)-(OK) ₂

RZ-3 C ₁₂ H ₂₅ OCH ₂ CH ₂ OP(=O)-(OK) ₂

RZ-4 C ₁₅ H ₃₁ (OCH ₂ CH ₂ ) ₅ OP(=O)-(OK) ₂

RZ-5 {C ₁₂ H ₂₅ O(CH ₂ CH ₂ O) ₅ } ₂ -P(=O)-OH

RZ-6 {C ₁₈ H ₃₅ (OCH ₂ CH ₂ ) ₈ O} ₂ -P(=O)-ONH ₄

RZ-7 (tC ₄ H ₉ ) ₃ -C ₆ H ₂ -OCH ₂ CH ₂ OP(=O)-(OK) ₂ RZ-8 (iso-C ₉ H ₁₉ -C ₆ H ₄ -O-(CH ₂ CH ₂ O) ₅ -P(=O)-(OK)(OH)

RZ-9 C ₁₂ H ₂₅ SO ₃ Na

RZ-10 C ₁₂ H ₂₅ OSO ₃ Na

RZ-11 C ₁₇ H ₃₃ COOH

RZ-12 C ₁₇ H ₃₃ COOH‧N(CH ₂ CH ₂ OH) ₃

RZ-13 iso-C ₈ H ₁₇ -C ₆ H ₄ -O-(CH ₂ CH ₂ O) ₃ -(CH ₂ ) ₂ SO ₃ Na

RZ-14 (iso-C ₉ H ₁₉ ) ₂ -C ₆ H ₃ -O-(CH ₂ CH ₂ O) ₃ -(CH ₂ ) ₄ SO ₃ Na

RZ-15 sodium triisopropyl naphthalene sulfonate

RZ-16 tris-t-butylnaphthalenesulfonate

RZ-17 C ₁₇ H ₃₃ CON(CH ₃ )CH ₂ CH ₂ SO ₃ Na

RZ-18 C ₁₂ H ₂₅ -C ₆ H ₄ SO ₃ ‧NH ₄

The addition amount of the release accelerator is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass, and most preferably 0.1 to 0.5% by mass based on the polyamine.

<Method for Producing Polyimine Film>

Specific examples of the method for producing the above polyamidamine film will be described below.

The method for producing a polyamidamine film of the present invention comprises the steps of preparing a mixture containing the aforementioned soluble polyamidamine and the inorganic fine particles (mixture preparation step), and producing a blend containing the foregoing mixture and the aforementioned polyamine and a solvent. a step of a foreign matter (a dopant preparation step), a step of forming a film by extending the dopant onto the support (the step of enlarging), and a step of evaporating the solvent in the film in the film on the support (solvent) The evaporation step), the step of peeling off the film from the support (peeling step), and the drying step of drying the peeled film are characterized.

The method for producing a polyamidamine film of the present invention comprises the steps of preparing a mixture containing the above-mentioned soluble polythinamide and the above-mentioned inorganic fine particles (mixture preparation step), and producing a blend containing the foregoing mixture and the aforementioned polyamine and a solvent a step of a foreign matter (a dopant preparation step), a step of forming a film by delaying the dopant on the support (extension step), a step of peeling off the film from the support (peeling step), drying the obtained film, drying the film, preparing a film (first drying step), stretching the dried film (extension step), and extending the film a step of drying the film again (second drying step), a step of winding up the obtained polyimide film (winding step), and, if necessary, heat-treating the film to subject the oxime to imidization (heating step) and the like are preferred.

Hereinafter, each step will be specifically described.

(mixture preparation step)

The mixture preparation step of the present invention comprises the step of preparing a mixture containing soluble polyamidos and inorganic fine particles having a solubility of 1 g or more with respect to 100 g of methylacetamide or 100 g of γ-butyrolactone at 60 °C.

The above-mentioned mixture may be any form as long as it contains soluble polyamidamine and inorganic fine particles, for example, a dopant containing the above-mentioned soluble polyamidamine and the aforementioned inorganic fine particles and a solvent, or It is preferred that the polyimine film containing the above-mentioned soluble polyimine and the above-mentioned inorganic fine particles is broken. It is preferred that the mixture is a crushed product obtained by crushing a polyimine film containing soluble polyimide and inorganic fine particles, and the deviation in the film thickness direction of the haze value is smaller.

When the mixture is a dopant containing the aforementioned soluble polyamidamine and the aforementioned inorganic fine particles and a solvent, the dissolved dopant is stored in 60 When the temperature is higher than °C for 2 hours or more, the turbidity deviation in the surface direction of the film can be made smaller, which is preferable.

<Crushed product obtained by crushing a polyimine film containing soluble polyamidamine and inorganic fine particles>

The mixture of the present invention is preferably obtained by crushing a polyimine film containing the above-mentioned soluble polyimine and the above-mentioned inorganic fine particles.

The crushed product preferably contains a mass ratio of 10 to 70% by mass based on the polyimide film. When it is 10% by mass or more, the difference in the haze value in the plane direction is preferably small, and when it is 70% by mass or less, it is preferable from the viewpoint of good transportability. Since the crushed product has good mixing property with the resin, it is preferable from the viewpoint of not causing turbidity deviation. However, since the effect of the inorganic fine particles is hard to be exhibited, the transporting effect is weak.

The crushed product may be used to cut the chips at both ends of the film roll during the drying or final stage of the polyimide film, the loss product generated in the condition adjustment after starting the operation, or the product cannot be formed due to an unexpected event. The fragments produced by the mesh or film are preferably used by the user.

When the mixture is reused, first, the film is broken into pieces of 0.5 to 40 mm, preferably 10 to 30 mm, using a crusher.

At this time, the debris is first removed from the static electricity to prevent the debris from sticking or blocking in the crusher, the agglomeration between the fragments, and the adhesion of the fragments to the wall surface.

The pulverized chips are transferred to a pipe using an air transport means such as a blower, temporarily stored in a storage container, and then the metered amount is used to measure the determined amount, and then it is put into a dissolution tank.

In the dissolution tank, the new soluble polyamine and the solvent are simultaneously stirred and dissolved by heating to prepare a dopant. After the dissolution is completed, the liquid is supplied using a liquid supply pump, and the impurities are filtered by a filter, and stored in the static storage tank 13 for defoaming.

In the present invention, in addition to the method of introducing the crushed product into the dissolution tank in a fragmented manner, for example, there is a method in which the crushed product is first dissolved in another substance and then introduced into the dissolution tank as a recovered solution.

(Doping production step)

In the method for producing a polymethyleneamine film of the present invention, a mixture containing the soluble polyamidamine and the inorganic fine particles and a new soluble polyamidamine are dissolved in a solvent to prepare a dopant, and a dopant is used. The dopant is preferably formed by a solution-precipitation film formation method. It is particularly preferable to prepare a dopant by dissolving a mixture of soluble polyamidamine and inorganic fine particles with a new soluble polyamidamine and a new inorganic fine particle in a solvent, and using the dopant to carry out a solution according to the solution. Film making method.

The solvent is preferably used as a main solvent using a low boiling point solvent having a boiling point of 80 ° C or less, which is preferable because it can be lowered in the production process temperature (particularly drying temperature) of the film, and the coloring or heat shrinkage ratio is lowered. The term "used as a main solvent" as used herein means that when the solvent is mixed, it is used in an amount of 55 mass% or more, preferably 70 mass%, based on the total amount of the solvent. More preferably, it is 80% by mass or more, and particularly preferably 90% by mass or more. Of course, if it is used alone, it is 100% by mass.

The low boiling point solvent may be any one which can dissolve the polyamidamine and other additives at the same time. For example, the chlorine solvent is dichloromethane, the non-chlorinated solvent is methyl acetate, ethyl acetate or amyl acetate. , acetone, methyl ethyl ketone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2, 3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1 1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n-propanol , iso-propanol, n-butanol, sec-butanol, tert-butanol, and the like.

Among them, a low boiling point solvent having a boiling point of 80 ° C or less is contained in the above solvent, and contains methylene chloride (40 ° C), ethyl acetate (77 ° C), methyl ethyl ketone (79 ° C), tetrahydrofuran (66). It is preferred that at least one solvent selected from the group consisting of acetone (56.5 ° C) and 1,3-dioxolane (75 ° C) as a main solvent (in the parentheses, the respective boiling points thereof).

In addition, when the solvent is mixed, the solvent contained in the solvent can be used as long as it can dissolve the polyiminamide of the present invention, and the solvent other than the solvent can be used, for example, N. -Methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethyl Formamide, N-methyl caprolactam, hexamethylene phosphamide, tetramethyl hydrazine, dimethyl hydrazine, m-cresol, phenol, p-chlorophenol, 2-chloro-4-hydroxyl Toluene, diethylene glycol diether, triethylene glycol diether, tetraethylene glycol diether, dioxane, γ-butyrolactone, dioxane Alkane, cyclopentanone, ε-caprolactam, chloroform, etc., may be used in combination of 2 or more types. Further, when used in combination with these solvents, a poor solvent such as hexane, heptane, benzene, toluene, xylene, chlorobenzene or o-dichlorobenzene does not allow the polyimide and the carbonyl group of the present invention to be used. The degree of precipitation of the organic compound is preferred for the user.

Further, an alcohol-based solvent which is selected from methanol, ethanol, or butanol to improve the peeling property and to allow high-speed extension can be preferably used. Among them, it is preferred to use methanol or ethanol. When the proportion of the alcohol in the dopant is too high, the mesh will be gelled and easily peeled off by the metal support.

The method for dissolving polymethyleneamine and other additives may be carried out by a method carried out under normal pressure, a method carried out below the boiling point of the main solvent, or a method of pressurizing at a boiling point or higher of the main solvent, and No. 9-95544 Various methods of dissolving, such as a method of performing a cooling and dissolving method described in Japanese Laid-Open Patent Publication No. Hei 9-95538, and a method of performing high pressure as described in JP-A-11-21379.

The prepared dopant can be filtered by introducing a filter through a liquid feeding pump or the like. For example, when the main solvent of the dopant is methylene chloride, the methylene chloride is at a boiling point of 1 atm. +5 ° C or higher, and the dopant is filtered to remove the gelatinous substance in the dopant. Impurities. The preferred temperature range is 45 to 120 ° C, preferably 45 to 70 ° C, and more preferably 45 to 55 ° C.

Further, it is more suitable to prepare a raw material of a resin used for a dopant by granulating a polyimine and other compounds in advance. user.

(Step of forming a flow-precipitating film)

The prepared dopant is sent to a mold through a liquid feeding pump (for example, a pressurized quantitative gear pump), and the dopant is extended by the mold to an infinitely movable endless support body. For example, a metal support such as a stainless steel transfer belt or a rotating metal drum is at a position where it is extended.

The metal support in the extension (molding) preferably has a surface treated by a mirror surface, and the support is preferably a metal support such as a stainless steel transfer belt or a plated surface of the cast. The width of the mold is in the range of 1 to 4 m, preferably in the range of 1.5 to 3 m, more preferably in the range of 2 to 2.8 m. Further, the support may be made of a non-metal one. For example, a polyethylene terephthalate (PET) film, a polyethylene naphthalate (PEN) film, or a polybutylene terephthalate (PBT) may be used. A film, a nylon 6 film, a nylon 6,6 film, a polypropylene film, a transfer belt of polytetrafluoroethylene or the like, and the like. As the polyamidene used as the flexible substrate, the metal support of the delayed flow polyamine or the polyimine on the film can be taken up.

The conveying speed of the metal support is not particularly limited, and is usually in the range of 5 m/min or more, preferably 10 to 180 m/min, and particularly preferably 80 to 150 m/min. The higher the transport speed of the metal support, the more easily the co-admixed gas is generated, so that the film thickness unevenness is remarkably generated due to uneven appearance.

The conveying speed of the metal support refers to the moving speed of the outer surface of the metal support.

The surface temperature of the metal support is preferably as the drying speed of the flow film is higher as the temperature is higher, but the film is too high, and the film is foamed and flattened, so that it is used. The boiling point of the solvent is preferably in the range of from -50 to -10 °C.

In the mold, the vertical cross section in the width direction has a shape that is tapered toward the discharge port. The mold usually has a tapered surface on the downward flow side and the upstream side in the conveying direction of the lower portion, and the discharge port between the tapered surfaces is in the shape of a slit. The mold is preferably made of a metal, and specific examples thereof are, for example, stainless steel, titanium, or the like. In the present invention, when manufacturing films having different thicknesses, it is not necessary to change the molds having different gap gaps.

The mold is preferably a pressure mold which can easily form a uniform film thickness by adjusting the slit shape of the mold portion of the mold. The press mold, for example, has a coat hanger die or a T-die, and the like can be used. Even when a film having a different thickness is continuously produced, the discharge amount of the mold can be maintained at a certain value. Therefore, when a press mold is used, conditions such as extrusion pressure and shear rate can be maintained at a certain value. Further, for the purpose of increasing the film forming speed, two or more press molds may be provided on the metal support, and the amount of the dopant may be divided and then laminated.

(solvent evaporation step)

The solvent evaporation step is performed on the metal support, and is a pre-drying step of heating the flow-preventing film on the metal support to evaporate the solvent.

a method of evaporating a solvent, for example, using a dryer to delay The method of blowing the heated air on the side of the film side and the inside of the metal support, the method of conducting heat by using the heated liquid from the inner surface of the metal support, the method of using the radiant heat to conduct heat from the surface, and the like. It is also preferable to combine them appropriately and combine them. The surface temperature of the metal support is preferably the same as the whole, and the difference may be due to the position. The temperature of the heated air is preferably in the range of 10 to 220 °C.

The temperature of the heated air (drying temperature) is preferably 200 ° C or less, more preferably 140 ° C or less, and still more preferably 120 ° C or less.

In the solvent evaporation step, the dry film is preferably dried in such a manner that the amount of the residual solvent is in the range of 10 to 150% by mass in terms of the peeling property of the film and the transportability after peeling.

In the present invention, the amount of residual solvent can be expressed by the following formula.

Residual solvent amount (% by mass) = {(M - N) / N} × 100

Here, M is the mass of the retardation film (film) at a specific time point, and the mass of N is M at 200 ° C and dried for 3 hours. In particular, in the solvent evaporation step, when the amount of residual solvent reached is calculated, M is the mass of the retardation film before the stripping step.

(peeling step)

A step of peeling off the film from the peeling position on the metal support by the evaporation of the solvent.

The peeling tension at the time of peeling the film on the metal support is usually in the range of 60 to 400 N/m, but wrinkles are likely to occur at the time of peeling, and the peeling is performed under a tension of 190 N/m or less. good.

In the present invention, the temperature of the peeling position on the metal support body The degree is preferably in the range of -50 to 60 ° C, preferably in the range of 10 to 40 ° C, and preferably in the range of 15 to 40 ° C.

The stripped film after stripping (also known as a film after stripping) can be sent directly to the stretching step, or when the desired amount of residual solvent is achieved, it can be sent to the first drying step before being sent. The extension step is also possible. In the present invention, it is preferable to carry out the step of stably transporting in the stretching step, and it is preferred that the film is sequentially sent to the first drying step and the stretching step after the peeling step.

(first drying step)

The first drying step is a drying step of heating the film and evaporating the solvent. The drying means is not particularly limited, and for example, hot air, infrared rays, a heating roller, a microwave, or the like can be used. From the viewpoint of simplicity, it is preferable to use a roll transport film in which a cross arrangement is disposed, and dry it by hot air or the like. The drying temperature is preferably in the range of 30 to 200 ° C in consideration of the amount of residual solvent and the expansion ratio during transportation.

The drying temperature is preferably 200 ° C or lower, preferably 140 ° C or lower, and more preferably 120 ° C or lower.

When the drying temperature is low, the heat shrinkage rate of the film can be increased.

(extension step)

When the film which has been peeled off from the metal support is stretched, the film thickness, flatness, alignment property, and the like of the film can be controlled.

In the method for producing a film of the present invention, the length direction is It is better to extend in the width direction.

The extension operation can also be divided into a multi-stage implementation. Further, in the case of biaxial stretching, the two-axis stretching may be performed simultaneously or in a stepwise manner. In this case, the staged means that, for example, the extension different from the extension direction can be sequentially performed, the extension of the same direction is divided into multiple stages, and the extension of the different directions can be added to any of the stages.

That is, for example, an extended state such as the following can be performed:

‧ extend in the length direction → extend in the width direction → extend in the length direction → extend in the length direction

‧ Extend in the width direction → Extend in the width direction → Extend in the length direction → Extend in the length direction

Further, the state of the simultaneous biaxial stretching also includes the case of extending in one direction, and the other direction is for relaxing the tension to form a contraction. Preferably, the stretching ratio is extended in the width direction and the length direction by a range of ×1.01 times to 1.5 times. Here, the term "expansion ratio" means (the length of the film after stretching or the length of the length) / (the length of the film before stretching or the length of the length).

The amount of residual solvent at the start of stretching is preferably in the range of 0.1 to 200% by mass.

When the amount of the residual solvent is 0.1% by mass or more, the effect of improving planarity can be obtained by stretching, and when it is 200% or less, stretching is easy.

The method for producing the polyimide film of the present invention may preferably extend in the longitudinal direction or in the width direction, preferably in the width direction, so that the film thickness after stretching can reach a desired range. Relative to poly The glass transition temperature (Tg) of the melamine film is preferably extended in a temperature range of (Tg-200) to (Tg + 100) °C. When extending in the above temperature range, the turbidity can be lowered because the elongation stress can be lowered. Further, it is possible to suppress the occurrence of cracking, and it is possible to obtain a polyimide film having excellent planarity and having a good coloring property of the polyimide film itself. The extension temperature is preferably in the range of (TgL - 150) to (TgH + 50) °C.

In the method for producing a polyimide film of the present invention, a self-supporting film which is peeled off from the support can be extended in the longitudinal direction by a stretching roller at a predetermined conveying speed.

For the method of drying in the width direction, a drying method in which all the drying treatments or partial drying treatments are performed in a state in which both ends of the width of the film are kept in the width direction by using a jig or a needle as disclosed in JP-A-62-46625 (Also known as tentering method), in which the tentering method using the jig is preferred.

The film extending in the longitudinal direction or the unstretched film can be introduced into the tenter in a state in which the both ends of the width direction are clamped by the jig, and the tenter and the jig are simultaneously conveyed in the width direction. good.

When extending in the width direction, it is preferable to extend the film at a stretching speed in the range of 50 to 1000%/min in the width direction from the viewpoint of improving the planarity of the film.

When the stretching speed is 50%/min or more, the film properties can be improved, and the film can be processed at a high speed. Therefore, from the viewpoint of production suitability, when the film is 1000%/min or less, the film can be prevented from being broken. It is preferred to carry out the treatment.

Preferably, the stretching speed is in the range of 100 to 500%/min. The extension speed can be defined by the following formula.

Extension speed (%/min) = [(d ₁ /d ₂ )-1]×100(%)/t

(In the above formula, d ₁ is the width dimension of the extending direction of the resin film after stretching, d ₂ is the width dimension of the extending direction of the resin film before stretching, and t is the time (min) required for stretching).

In the extension step, it is usually carried out in a manner of maintaining and easing after the extension. That is, in this step, it is preferable to carry out the steps of extending the stretching film, maintaining the film in the extended state, and relaxing the film in the extending direction. The maintenance phase is to extend the extension temperature in the extension phase in accordance with the extension of the extension ratio achieved in the extension phase. In the mitigation phase, after the extension in the extension phase is maintained in the maintenance phase, the tension of the extension is released, and the extension is relaxed. The relaxation phase can be carried out at temperatures below the extension temperature in the extension phase.

(2nd drying step)

Next, the stretched film is heated and dried. When the film is heated by hot air or the like, a nozzle capable of exhausting may be provided to discharge the hot air (a solvent-containing gas or a gas containing moisture) after use, thereby avoiding the step of mixing the hot air after use. The hot air temperature is preferably in the range of 40 to 350 °C. Further, the drying time is preferably from about 5 seconds to 30 minutes, preferably from 10 seconds to 15 minutes.

Moreover, the heating and drying means is not limited to hot air, for example. For example, infrared rays, a heating roller, a microwave, or the like can be used. From the viewpoint of simplicity, it is preferred to use a hot air or the like for drying the roll transport film in which the cross shape is disposed. When the drying temperature is in the range of 40 to 150 ° C, it is preferable to carry out a large heat shrinkage. It is preferably 40~120 °C.

In the second drying step, it is preferred to dry the film so that the amount of the residual solvent is reduced to 0.5% by mass or less.

(rolling step)

The winding step is a step of winding up the obtained polyimide film and cooling it to room temperature. The coiler can be generally used by a user. For example, a tension method, a calibrated wrench method, a tension method, and a program tension control for maintaining internal stress can be used. The winding method such as the roller method is taken up.

The thickness of the polyimide film is not particularly limited, and is preferably, for example, in the range of 1 to 200 μm, particularly 1 to 100 μm.

In the winding step, at the time of extension conveyance, slit processing may be performed on both ends of the polyimide film sandwiched between Tenter clips or the like. The cut end of the polyimide film can be carefully cut in the range of 1 to 30 mm in width, and then dissolved in a solvent, and it is preferable to recycle it.

The respective steps from the solvent evaporation step to the winding step may be carried out in an atmosphere or in a gas atmosphere of an inert gas such as a nitrogen gas. Again, in each step, especially the drying step or The extension step must first consider the critical concentration of the solvent in the gaseous environment before the explosion occurs.

(heating step)

After the winding step, the polyimide film dried in the second drying step can be further subjected to the purpose of imidating the polymer chain and the polymer chain to improve the mechanical properties. Heating step of heat treatment.

Further, the second drying step may have a heating step at the same time.

As the heating means, for example, a known means such as hot air, electric heater, microwave or the like can be used. An electric heater such as the above-described infrared heater can be used.

In the heating step, when the polyimide film is rapidly heated, the surface defects and the like are increased, so that the heating method should be appropriately selected. Moreover, the heating step is preferably carried out in a low oxygen atmosphere.

In the second drying step and the heating step, when the heating temperature exceeds 450 ° C, the energy required for heating is extremely large, so the manufacturing cost is increased, and the load on the environment is also increased, so the heating temperature is preferably 450 ° C or less. .

Further, after the winding step, the step of cutting the polyimide film from the end portion in the width direction may be performed before or after the heating step, and the step of removing static electricity may be performed when the polyimide film is electrostatically charged.

<Shape of polytheneamine film>

The polyimine film of the present invention preferably has a rectangular shape, specifically, a length in the range of about 100 to 10,000 m, which can be wound into a roll shape. Further, the width of the polyimide film of the present invention is preferably 1 m or more, more preferably 1.4 m or more, and particularly preferably 1.4 to 4 m.

<Use>

The polyamidamine film of the present invention can be used as a transparent film of an image display device. In particular, it is suitable as a flexible image display device. The device to be applied is not particularly limited, and examples thereof include an organic electroluminescence (EL) image display device, a liquid crystal image display device (LCD), an organic photoelectric conversion device, a touch panel, a polarizing plate, and a retardation film. From the viewpoint of obtaining the effect of the present invention more efficiently, it is preferable to use a flexible television projector as an organic electroluminescence (EL) image display device, a liquid crystal image display device (LCD), or the like, and a flexible display. Front face member.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the examples. In the examples, the expression "parts" or "%" is used, and unless otherwise specified, "mass parts" or "% by mass" are used.

[Example 1]

The structures of the compounds used in the examples are as set forth below.

Anhydride A: bicyclo[4.2.0]octane-3,4,7,8-tetracarboxylic dianhydride

Diamine compound B: 2,2'-dimethylbiphenyl-4,4'-diamine

Moreover, the acquisition of the commercial item of the said compound is as follows.

Anhydride 1: Daikin Industries Co., Ltd.

Anhydride 2: US Nike Co., Ltd.

Anhydride 3: DAICEL Co., Ltd.

Diamine 1: Daikin Industries Co., Ltd.

Diamine 2: Mitsui Precision Chemical Co., Ltd.

Diamine 6: Wakayama Jinghua Co., Ltd.

Diamine Compound B: Showa Chemical Co., Ltd.

<Production of Polyimine Film 101A (Polyimine Film for Mixture)> (Production of polyamidamine solution A)

17.87 g (57.6 mmol) of the above-mentioned acid anhydride 2 (manufactured by Minnesota Co., Ltd.) was added to N in a four-necked flask equipped with a dry gas introduction tube, a cooler, a Dean-Stark agitation device filled with toluene, and a stirrer. N-dimethylacetamide (134 g) was stirred under a nitrogen stream at room temperature.

Subsequently, 11.53 g (60 mmol) of the above-mentioned diamine 2 (manufactured by Mitsui Precision Chemical Co., Ltd.) was added thereto, and the mixture was heated and stirred at 80 ° C for 6 hours. Subsequently, the external temperature was heated to 190 ° C, and the water produced by the imidization of hydrazine was distilled off in azeotropic manner with toluene. After heating, refluxing, and stirring for 6 hours, the production of water was not confirmed. Subsequently, the toluene was distilled off, heated for further 7 hours, and then toluene was distilled off, and then re-precipitated by adding methanol to form a dimethyl methoxide solution having a solid content of 8% by mass to obtain a polytheneamine. Polyammonium solution A of resin A.

(Making the main dopant for the manufacture of broken products)

A main dopant of a fracture product having the following composition was produced. First, methylene chloride (boiling point 40 ° C) was added to a pressurized dissolution tank. The polyiminamide solution A and the residual components obtained above were placed in a pressurized dissolution vessel to which a solvent was added. Heat and stir it to dissolve it completely, then The main dopant used in the manufacture of the crushed product was obtained by filtering it using an Augmentation filter paper No. 244 made of a filter paper (strand).

(The composition of the main dopant used in the production of the broken product)

(Extension step)

Secondly, the endless belt extension device was used to uniformly spread the dopant on the stainless steel belt support at a temperature of 30 ° C and a width of 1500 mm. The temperature of the stainless steel conveyor belt was controlled at 30 °C.

(peeling step)

On the stainless steel belt support, the amount of residual solvent in the film of the cast (cast) was evaporated to 75%, and then peeled off from the stainless steel belt support under the conditions of a peeling tension of 180 N/m.

(extension step)

The peeled film was stretched by 1.40 times in a width direction of 100%/min using a jig tenter at a heat of 120 ° C. The amount of residual solvent at the start of elongation was 8% by mass.

(drying step)

The stretched film was dried at a drying temperature of 120 ° C under conditions of a conveying tension of 100 N/m and a drying time of 15 minutes until the residual solvent amount was less than 0.5% by mass to obtain a polythene having a dry film thickness of 51 μm. Amine film. The obtained polyamidamine film was taken up to obtain a polyimide film 101A for the mixture.

<Production of Polyimide Films 102A to 108A and 110A (Polyurethane Film for Mixing)>

In the process of producing the above-mentioned mixed polyimide film 101A, the mixing ratio of the type of the acid anhydride, the diamine, and the inorganic fine particles used is changed according to the contents shown in Table 2, and the others are mixed and mixed. In the same manner as the melamine film 101A, the mixed polyimide films 102A to 108A and 110A were obtained. Further, in the production of the polyimide films 101A to 108A and 110A for mixing, the acid anhydride and the diamine used as the raw material of the polyimide film are the compounds described in Table 1, and the polyaluminium is mixed with the polyimide. The amine film 101A uses the same molar amount.

Each of the above-mentioned polyimine films for mixing has a shape of a rectangular film having a width of 1900 mm and a length of 8000 m.

<Production of the drum bodies 101A to 108A and 110A>

The winding drum body of the above-mentioned mixed polyimide film 101A to 110A (width: 1900 mm, length: 8000 m) was obtained as the drum bodies 101A to 108A and 110A in accordance with the following winding conditions.

(volume conditions)

Touch roller: diameter 120mm, length 2600mm

Material of the touch roller: NBR rubber (made by Minghe Rubber Industry Co., Ltd.) White-Elecon

Hardness 35 degrees, thickness 10mm, CFRP (Carbon Fiber Reinforced Plastics) core

Touch pressure of the touch roller: 50N/m

Winding tension: initial tension 250N/m cone 90% angle 25%

Coiling speed: 100m/min

The diameter of the take-up shaft: 15.24cm

Material of the take-up shaft: FRP (Fiber Reinforced Plastics)

(production of broken products)

The drum bodies 101A to 108A and 110A are made of a film from both end portions in the width direction, and are crushed by a crusher to obtain pieces of 10 to 30 mm in size, which are respectively used as crushed products 101A to 108A and 110A.

<Production of Polyimine Film 101> (Production of polyamidamine solution A)

Into a four-necked flask equipped with a dry nitrogen gas introduction tube, a cooler, a Dean-Stark agitation device filled with toluene, and a stirrer, 17.87 g (57.6 mmol) of the above-mentioned acid anhydride 2 (manufactured by Minaco Co., Ltd.) was added to N, N. To the dimethylacetamide (134 g), the mixture was stirred under a nitrogen stream at room temperature.

Thereto, 11.53 g (60 mmol) of the above-mentioned diamine 2 (manufactured by Mitsui Precision Chemical Co., Ltd.) was added, and the mixture was stirred under heating at 80 ° C for 6 hours. Subsequently, the external temperature was heated to 190 ° C, and the water produced by the imidization of hydrazine was simultaneously subjected to azeotropic distillation with toluene. The result of heating, refluxing, and stirring for 6 hours did not confirm the production of water. Subsequent to the distillation of toluene, heating was continued for 7 hours. Further, methanol is poured into a solution obtained by distilling off toluene to reprecipitate it to form a dimethyl acid solution containing 8 parts by mass of the solid component after drying, thereby preparing a polyamidamine solution A containing polyamidamine resin A. .

(production of dopants)

A main dopant having the following composition was produced. First, methylene chloride (boiling point 40 ° C) was added to a pressurized dissolution tank. The polyiminamide solution A obtained above and the remaining components were placed in a pressurized dissolution tank of the solvent under stirring. After heating, stirring, and completely dissolving, it was filtered using Angstrom filter paper No. 244 made of filter paper (strand) to obtain main doping. Things.

(composition of the main dopant)

This main dopant is used as the main dopant 101. The crushed product 101A was added to the main dopant 101 so that the mass ratio of the mixture was 5% by mass, and the mixture was again dissolved and dissolved.

Further, in the mass ratio of the mixture, the mass (X) of the polyamidamide resin in the main dopant 101 used for mixing, and the mass of the polyamidamide resin in the crushed product 101A used for mixing (Y) In the total, the mass (Y) ratio of the polyamidamide resin in the crushed product 101A used for mixing is represented by the use % by mass.

(Extension step)

Secondly, the endless conveyor belt extension device was used to uniformly spread the dopant on the stainless steel conveyor belt support having a temperature of 30 ° C and a width of 1500 mm. The temperature of the stainless steel conveyor belt was controlled at 30 °C.

(peeling step)

On the stainless steel conveyor belt support, the amount of residual solvent in the film that evaporates the solvent to the extended flow (casting) reaches 75%, and secondly, the peeling tension is used. 180 N/m, peeled off from the stainless steel belt support.

(extension step)

The peeled film was stretched 1.40 times in a width direction and an elongation speed of 100%/min using a jig tenter which applied heat of 120 °C. The amount of residual solvent at the start of the elongation was 8% by mass.

(drying step)

The stretched film was dried at a drying temperature of 120 ° C to a residual temperature of less than 0.5% by mass under the conditions of a transport tension of 100 N/m and a drying time of 15 minutes to obtain a polyimine film having a dry film thickness of 51 μm. The obtained polyamidamine film was taken up to obtain a polyimide film 101.

<Production of Polyimine Film 102~110>

In addition to the production of the polyimide film 101 described above, the acid anhydride, the type of the diamine, the mass ratio of the inorganic fine particles, and the mass ratio of the mixture are changed according to the contents shown in Table 2, and the others are mixed. Polyimide film 102 to 110 was obtained by the same method using polymethyleneamine film 101. Further, in the production of the polyimide film 101 to 110, the acid anhydride and the diamine which are the raw materials of the polyimide film to be used are the compounds described in Table 1, and are used in the same manner as the polyimide film 101. The amount of Mo.

Each of the above polyimine films was formed into a rectangular film having a width of 1900 mm and a length of 8000 m.

<Production of the drum body 101 to 110>

The above-mentioned polyimide film 101 to 110 (width: 1900 mm, length: 8000 m) was taken up from the drum body, and the drum bodies 101 to 110 were obtained under the following winding conditions.

(volume conditions)

Touch roller: diameter 120mm, length 2600mm

Material of the touch roller: NBR rubber (made by Minghe Rubber Industry Co., Ltd.) White-Elecon

Hardness 35 degrees, thickness 10mm, CFRP (Carbon Fiber Reinforced Plastics) core

Touch roller pressure: 50N/m

Winding tension: initial tension 250N/m cone 90% angle 25%

Coiling speed: 100m/min

The diameter of the take-up shaft: 15.24cm

Material of the take-up shaft: FRP (Fiber Reinforced Plastics)

(solubility)

Each of the polyamidoamines used in the production of the polyimide film was measured for the upper limit of dissolution when it was dissolved in 100 g of dimethylacetamide at 60 °C.

(turbidity)

Turbidity (full turbidity) is based on JIS K 7136 and is measured using a turbidity meter. The NDH 2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the polyimide film of each of the roller bodies, and was evaluated according to the following criteria. The light source of the turbidity meter is a halogen ball using 5V9W, and the light receiving portion is a fluorescent battery (with a specific sensitivity filter). The measurement of turbidity was carried out under the conditions of 23 ° C ‧ 55% RH.

(deviation of the turbidity value in the plane direction (standard deviation))

A polyimide film having a width of 1900 mm was used. The measurement of the haze value was carried out at intervals of 10 mm per 10 mm in the width direction of the drum body. This measurement was performed using three drum bodies, and the total was measured for turbidity at 285 points.

The standard deviation of the turbidity value of 285 points was calculated, and the deviation (standard deviation) of the turbidity value in the plane direction was measured. After the standard deviation is determined, the deviation is evaluated according to the following evaluation criteria.

◎: The standard deviation of the turbidity value in the plane direction is less than 0.3.

○: The standard deviation of the turbidity value in the plane direction is 0.3 or more and less than 0.6.

×: The standard deviation of the turbidity value in the plane direction is 0.6 or more

(transportability)

The transport properties of the polyimide film of each of the drum bodies were evaluated in the following manner.

When it is transported at a repetitive output tension of 100 N/m and a take-up tension of 150 N/m, it is evaluated in the drum and is in contact with the film. In the width of 2 m (mirror surface), the amount of snakes in 10 minutes was evaluated at a position of 50 cm between the transport rollers.

◎: The amount of snakes is less than 3mm (qualified)

○: The amount of snakes is more than 3mm, and the amount of snakes is less than 5mm (qualified)

×: The amount of snakes is higher than 5mm (failed)

The composition of each polyamine film and the deviation (standard deviation) of the transport direction from the surface direction of the turbidity value are shown in Table 2.

As shown in Table 2, it was found that the polyimine film of the present invention is a polyimide film having a small deviation (standard deviation) in the plane direction of good transportability and haze value.

[Example 2]

The flexurity of the polyimide film 101 and the polyimide film 109 of Example 1 was evaluated in the following manner.

(flexibility)

The flexural fatigue test (foil deflection test) of the obtained polyimide film was carried out in accordance with a flex fatigue tester prescribed in JIS C5016. In addition, under the condition that the deflection radius is 2.5 mm, the deflection speed is 2000 times/min, and the deflection stroke is 25 mm, the wiring forming surface at the time of deflection is the outer side, and is repeatedly bent in the same direction, and is set in the same direction. The number of deflections (the number of flexing resistances) from the outer side of the deflection direction to the broken line.

◎: 5000 times or more

○: 1000 times or more, less than 5,000 times

×: less than 1000 times

The results of the flexural resistance evaluation are shown in Table 3.

As shown in Table 3, it was found that the polyimide film of the present invention can improve the flex resistance.

[Example 3]

In the process of producing the main dopant according to the method for producing the polyimide film 101 of Example 1, the following mixed dopant 301A was used instead of the crushed product 101A, and the mixture was added in accordance with the mass ratio of the mixture shown in Table 4. The polyimide film 301 was obtained by the same method as the polyamidamide film 101.

(Manufacture of dopant dopant 301A) (Production of polyamine reaction solution 301A)

Into a four-necked flask equipped with a dry nitrogen gas introduction tube, a cooler, a Dean-Stark agitation device filled with toluene, and a stirrer, 17.87 g (57.6 mmol) of the above-mentioned acid anhydride 2 (manufactured by Minaco Co., Ltd.) was added to N, N. - Dimethylacetamide (134 g), and stirred under a nitrogen stream at room temperature.

11.53 g (60 mmol) of the above-mentioned diamine 2 (manufactured by Mitsui Precision Chemical Co., Ltd.) was added thereto, and the mixture was heated and stirred at 80 ° C for 6 hours. Subsequently, heating was continued until the external temperature reached 190 ° C, and water produced by the imidization of hydrazine was distilled off by azeotropy with toluene. After heating, refluxing, and stirring for 6 hours, it was confirmed that no water was generated. After continuously distilling off the toluene, heating for 7 hours, and then distilling off the toluene, the methanol was put into a reprecipitation to form a methylene chloride solution containing the solid component in an amount of 8 mass% after drying, thereby preparing a polyaluminum containing polyfluorene. A polyamidamine solution A of the amine resin A.

(Production of dopant dopant 301A)

A main dopant having the following composition was fabricated. First, dichloromethane (boiling point 40 ° C) was added to a pressurized dissolution tank. The polyiminamide solution A obtained above and the remaining components were put into a pressurized dissolution tank of a solvent under stirring. This was heated, stirred, and completely dissolved, and filtered using an filter paper No. 244 made of a filter paper (strand) to prepare a main dopant.

(Composition of the doping 301A for mixing)

The polyimide film 301 obtained in this manner, and the polyimide film 101 and the polyimide film 109 prepared in Example 1, were evaluated for transportability in the same manner as in Example 1. Deviation in the direction of the numerical direction (standard deviation).

The results are shown in Table 4.

It was found that the effects of the present invention can be attained even if the mixing dopant shown in Table 4 is used.

Further, it has been found that the use of a polyimide film of a broken product shows a greater effect.

[Example 4]

In addition to the use of the inorganic fine particles (manufactured by Japan AEROSIL Co., Ltd.) shown in Table 5, the inorganic fine particles (AEROSIL R972V, manufactured by Japan AEROSIL Co., Ltd.) used in the production of the polyimide film 101 of Example 1 were replaced. Polyimide films 401 to 405 were obtained in the same manner as in Example 1 except that the polyimide film 101 was used in the same manner as in the case of the polyimide film 101.

In the same manner as in Example 1, the polyimide film 101 and the polyimide film 401 to 405 were measured for the deviation (standard deviation) of the turbidity value of the transport property and the surface method.

The results are shown in Table 5.

As shown in Table 5, the modified inorganic fine particles were found to improve the effects of the present invention. Further, the smaller the average particle diameter of the primary particles of the inorganic fine particles, the more the effect of the present invention can be enhanced.

[Industrial use]

The method for producing a polyamidamine film of the present invention is suitable for a polyimide film having good transportability and a low variation in turbidity value in the surface direction of the film, so that the polyimide film is suitable for use. Used for small to large components for flexible displays.

Claims (5)

The invention relates to a method for producing a polyamidamine film, which comprises a poly-imine and an inorganic fine particle which dissolves 1 g or more with respect to 100 g of dimethylacetamide or 100 g of γ-butyrolactone at 60 ° C. A method for producing a guanamine film, comprising the steps of: preparing a mixture containing the polyimine and the inorganic fine particles, and preparing a dopant containing the mixture and the polyamine and a solvent; a step of forming a film by stretching the dopant on the support, a step of peeling the film from the support, and a drying step of drying the peeled film. The method for producing a polyimine film according to claim 1, wherein the mixture is a crushed product obtained by crushing a polyimine film containing the polyimine and the inorganic fine particles. The method for producing a polyimide film according to claim 1, wherein the mixture is a dopant containing the polyimine and the inorganic fine particles and a solvent. The method for producing a polyimide film according to any one of claims 1 to 3, wherein the mixture contains a mass ratio of 10 to 70% by mass based on the obtained polyimide film. A polyimide film characterized by dissolving 1 g or more of polymethyleneamine and inorganic fine particles in 100 g of dimethylacetamide or 100 g of γ-butyl lactone at 60 ° C, and The standard deviation of the surface direction of the turbidity value is 1 or less.