JP2006056956A - Method for producing polyimide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyimide film, with which the residual amounts of an organic solvent and a catalyst compound used in production of a polyimide by imidation reaction under a mild condition in the conventionally known preparation of a polyimide through an ordinary polyamic acid are small. <P>SOLUTION: The method for producing a polyimide film comprises using a solution consisting of a polyamic acid and a catalyst compound capable of conducting an acid-base interaction with the polyamic acid by a film casting method to form a film, immersing the obtained film in a liquid in which the catalyst compound in the solution and the film-forming solvent are soluble and drying the film. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a method for producing a polyimide film. Specifically, in the preparation of polyimide via a conventional polyamic acid known in the past, the organic solvent used in producing the polyimide from the imidization reaction under milder conditions and the polyimide film with a small residual amount of the catalyst compound It relates to a manufacturing method.

Since many common polyimides are insoluble in solvents, they are processed in the state of solvent-soluble polyamic acid, for example, cast on a substrate and heated to form a film-like polyimide. Cannot be completely imidized unless heated above the glass transition temperature (Tg) of the resulting polyimide. Therefore, the higher the Tg polyimide having excellent heat resistance, the higher the imidization conditions required.
For example, in applications such as passivation films and shielding films that require high Tg heat resistance used in solutions for semiconductor applications, etc., a solution made of polyamic acid as a precursor is applied, and heat treatment is performed at a high temperature of 300 ° C. or higher. Is converted to polyimide.
However, since a heat treatment at a high temperature of 300 ° C. or higher is necessary, damage to other portions is likely to occur, a material for which imidization is completed at a lower temperature has been desired because of limited applications.
As a method for imidizing polyamic acid at a relatively low temperature, it has been reported that imidization is completed at low temperature by adding an additive such as an imidization accelerator 4-hydroxypyridine or imidazole to a polyamic acid solution. (JP-A-9-302225, JP-A-2004-115813). However, in these methods, there is a problem that the imidization accelerator must be added in an equal amount or more with respect to the carboxylic acid of the polyamic acid, and the imidization accelerator remains in the polyimide film. In addition, when trying to produce a polyimide film exceeding several tens of μm by imidizing at a low temperature, there is a problem that not only the imidization accelerator but also the solvent used for film formation remains.
JP 9-302225 A JP-A-2004-115813

The present invention has been made against the background of the prior art, and provides a polyimide film in which imidization is performed at a lower temperature than in the prior art and no catalyst component or solvent component remains in the resulting polyimide film.

A polymer having a repeating unit represented by the following general formula (A) (hereinafter referred to as “polyamic acid”) is produced by a casting method using a solution comprising a catalyst compound capable of acid-base interaction with the polyamic acid. The present invention provides a method for producing a polyimide film, wherein the film is dipped in a solution in which the catalyst compound or the film-forming solvent is soluble, and then the film is dried.

・・・一般式（Ａ）
｛一般式（Ａ）において、Ｘは四価の有機基であり、Ｙは二価の有機基を示す。｝

... General formula (A)
{In General Formula (A), X represents a tetravalent organic group, and Y represents a divalent organic group. }

The present invention is described in detail below.
Among the catalyst compounds used in the present invention, the nitrogen-containing basic compound has a pKa (25 ° C. in water) which is an acid dissociation constant of its conjugate acid in the range of 0 to 13, preferably 2 to 13, and The compound is preferably 2.5 to 13, and is a compound capable of acid-base interaction with the carboxyl group of the polyamic acid.
Specific examples include aliphatic amines such as n-butylamine, n-amylamine, tert-butylamine, ethylenediamine, and benzylamine, and alkyl-substituted products thereof and derivatives thereof.
Imidazole, pyrazole, triazole, tetrazole, benzimidazole, naphthimidazole, indazole, benzotriazole, purine, imidazoline, pyrazoline, pyridine, quinoline, isoquinoline, dipyridyl, diquinolyl, pyridazine, pyrimidine, pyrazine, phthalazine, quinoxaarine, quinazoline, cinnoline, naphthyridine , Acridine, phenanthridine, benzoquinoline, benzoisoquinoline, benzocinnoline, benzophthalazine, benzoquinoxaline, benzoquinazoline, phenanthroline, phenazine, carboline, perimidine, triazine, tetrazine, pteridine, oxazole, benzoxazole, isoxazole, benzoisoxazole , Thiazole, benzothiazole, oxadia , Thiazole, pyrroledione, indoledione, pyrrolidinedione, benzoisoquinolidine, hexamethylenetetramine, pyrrolidine, 1,2-dimethylpyrrolidine, n-methylpyrrolidine, cyclohexylamine, n-butylcyclohexylamine, piperazine, 2, 5-dimethylpiperazine, piperidine, 1,2-dimethylpiperidine, 2,5-diazabicyclo [2,2,1] heptane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,4- Nitrogen-containing heterocyclic compounds such as diazabicyclo [2,2,2] octane, 1,8-diazabicyclo [5,4,0] -7-undecene, 4-aminopyridine, 4-methylaminopyridine, 4-hydroxypyridine and the like; Examples thereof include alkyl-substituted products and derivatives thereof.

Next, the substituted or unsubstituted amino acid compound used as the catalyst compound is not particularly limited, but examples thereof include unsubstituted amino acid compounds such as glycine, sarcoxin, phenylglycine, glutamic acid, and leucine, and compounds in which these amino groups are substituted. Is mentioned.
Then, the compound which consists of an aromatic hydrocarbon compound or an aromatic heterocyclic compound which has at least 2 or more hydroxyl groups of molecular weight 1000 or less used as a catalyst compound is demonstrated. The compound is not particularly limited, but if the molecular weight exceeds 1000, the vaporization point (boiling point, sublimation point, decomposition point) becomes too high, and it remains undesirably in the film.
In the present invention, these catalyst compounds may be used alone or in combination of two or more.

Although the catalyst compound used for this invention is based also on the catalyst compound to be used, it is 4 equivalents or less with respect to the carboxyl group of polyamic acid, Preferably it is 2.5-0.01 equivalent.
If the amount of the catalyst compound is too small, imidization is insufficient with low-temperature heat treatment, and if too large, the storage stability of the varnish is deteriorated and the film properties of the polyimide film are deteriorated.

  The polyamic acid used in the present invention is obtained by reacting diamine and tetracarboxylic dianhydride. Here, examples of the diamine and tetracarboxylic dianhydride used are as follows.

(Diamine)
Specific examples include 4,4'-diaminodiphenylpropane, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, and benzidine. 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl ether, 3,3'- Diaminodiphenyl ether, 4,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 4,4'-diamino-2,2'-trifluoromethylbiphenyl, 3,3'-diamino-2,2'- Trifluoromethylbiphenyl, 1,1-metaxylylene diene Amine, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1 , 1,3,3,3-hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 3,5-diamino-1-[(4-trifluoromethyl) phenoxyphenyl] benzamide, 1- [ 2,2-bis (trifluoromethyl) -3,3,4,4,5,5,5-heptafluoropentyl] -3,5-diaminobenzene, 1,4-diaminoanthraquinone, 1,5-diamino Anthraquinone, 1,5-diaminonaphthalene, bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenoxy) fluorene, 9,9-bis [4- (4-aminophenoxy) fur Enyl] fluorene, 9,9-bis [4- (4-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-aminophenoxy) -3-phenylphenyl] fluorene, 9-bis [4- (2-aminophenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (4-amino-3-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9, 9-bis [4- (4-amino-2-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (3-amino-4-trifluoromethylphenoxy) -3-phenyl Phenyl] fluorene, 9,9-bis [4- (3-amino-5-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9, -Bis [4- (3-amino-6-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-3-trifluoromethylphenoxy) -3-phenylphenyl Fluorene, 9,9-bis [4- (2-amino-4-trifluoromethylphenoxy) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-5-trifluoromethylphenoxy) ) -3-phenylphenyl] fluorene, 9,9-bis [4- (2-amino-6-trifluoromethylphenoxy) -3-phenylphenyl] fluorene and the like, and lower alkyl, aryl and aralkyl of these aromatic rings , Aromatic diamines such as halogen, alkyl halide, or substituted aryl halide groups,
1,3-bis (4-aminophenyl) adamantane, 1,3-bis [4- (4-aminophenoxy) phenyl] adamantane, 1,6-bis (4-aminophenyl) diamantane, 1,6-bis [ 4- (4-aminophenoxy) phenyl] diamantane, 4,9-bis (4-aminophenyl) diamantane, 4,9-bis [4- (4-aminophenoxy) phenyl] diamantane, tetrahydrodicyclopentadienylene Amine, hexahydro-4,7-methanoin danylene dimethylenediamine, 5-amino-1,3,3, -trimethylcyclohexanemethylamine (also known as isophoronediamine), 1,4-cyclohexanediamine, 4,4′-methylenebis (Cyclohexylamine) and its 3,3′-dimethyl substituted bis (aminomethyl) bicyclo [2.2 1] Heptane, 1,3-diaminoadamantane, 3,3′-diamino-1,1′-biadamantyl, 4,4′-hexafluoroisopropylidenebis (cyclohexylamine) 4,4′-hexafluoroisopropylidene Bis (cyclohexylamine))
1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, tetrahydrodicyclopentadienylenediamine, hexahydro Aliphatic and cycloaliphatic diamines such as -4,7-methanoin danylene dimethylene diamine, tricyclo [6,2,1,0 ^2.7 ] -undecylenedimethyl diamine;
Mono-substituted phenylenediamines represented by the following formula (III); diaminoorganosiloxanes represented by the following formula (IV);

（式中、Ｒ⁵は、−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−および−ＣＯ−から選ばれる２価の有機基を示し、Ｒ⁶は、ステロイド骨格またはトリフルオロメチル基を有する１価の有機基を示す。）

(Wherein R ⁵ represents a divalent organic group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁶ represents a steroid skeleton or A monovalent organic group having a fluoromethyl group is shown.)

（式中、Ｒ⁷は炭素数１〜１２の炭化水素基を示し、複数存在するＲ⁷は、それぞれ同一でも異なっていてもよく、ｐは１〜３の整数であり、ｑは１〜２０の整数である。）
下記式（９）〜（１３）で示される化合物などを挙げることができる。

(Wherein R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ⁷ may be the same or different, p is an integer of 1 to 3, and q is 1 to 20) Is an integer.)
Examples include compounds represented by the following formulas (9) to (13).

（式中、ｙは２〜１２の整数であり、ｚは１〜５の整数である。）

(In the formula, y is an integer of 2 to 12, and z is an integer of 1 to 5.)

Examples of the compound represented by the above formula (III) also include compounds represented by the following formulas (14) to (19).

これらのジアミン化合物は、単独でまたは２種以上組み合わせて用いることができる。

These diamine compounds can be used alone or in combination of two or more.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride include the following compounds.
Pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3 ′ -Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis ( 2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3 , 4-Dicarbo Cyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride,
3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetra Carboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4, 4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether Anhydride, bis (triphenyl phthalic acid) -4,4'-diphenylmethane dianhydride,
9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) phenyl] fluorene dianhydride, 2, 3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 9,9- Bis [4- (3,4-dicarboxyphenoxy) -3-phenylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -3-phenylphenyl] fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-phenylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2- Enylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-methylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-di Carboxyphenoxy) -3-methylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-methylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-methylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-ethylphenyl] fluorene dianhydride, 9-bis [4- (2,3-dicarboxyphenoxy) -3-ethylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-ethyl Enyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-ethylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxy) Phenoxy) -3-propylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -3-propylphenyl] fluorene dianhydride, 9,9-bis [4- ( 3,4-dicarboxyphenoxy) -2-propylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-propylphenyl] fluorene dianhydride, 9,9 -Bis [4- (3,4-dicarboxyphenoxy) -3-butylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxyphenoxy) -3-butylphenol Enyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-butylphenyl] fluorene dianhydride, 9,9-bis [4- (2,3-dicarboxy) Phenoxy) -2-butylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -3-t-butylphenyl] fluorene dianhydride, 9,9-bis [4 -(2,3-dicarboxyphenoxy) -3-t-butylphenyl] fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) -2-t-butylphenyl] fluorene di Anhydrous, aromatic tetracarboxylic dianhydrides such as 9,9-bis [4- (2,3-dicarboxyphenoxy) -2-t-butylphenyl] fluorene dianhydride,
Butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2 , 3,4,5-Tetrahydrofurantetracarbo Acid dianhydride, 1,3,3a, 4,5,9b-hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,3,3a, 4,5,9b-Hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,3,3a, 4,5,9b-Hexahydro-5-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,3,3a, 4,5,9b-Hexahydro-7-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -na [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl)- Naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5-dioxo-3-furanyl ) -Naphtho [1,2-c] -furan-1,3-dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, Bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, represented by the following formula (I) and And aliphatic and alicyclic tetracarboxylic dianhydrides such as compounds represented by (II);

（式中、Ｒ¹およびＲ⁴は、芳香環を有する２価の有機基を示し、Ｒ²およびＲ³は、水素原子またはアルキル基を示し、複数存在するＲ²およびＲ³は、それぞれ同一でも異なっていてもよい。）、
エチレングリコール−ビス（アンヒドロトリメリテート）、プロピレングリコール−ビス（アンヒドロトリメリテート）、１,４−ブタンジオール−ビス（アンヒドロトリメリテート）、１,６−ヘキサンジオール−ビス（アンヒドロトリメリテート）、１,８−オクタンジオール−ビス（アンヒドロトリメリテート）、２,２−ビス（４−ヒドロキシフェニル）プロパン−ビス（アンヒドロトリメリテート）、下記式（１）〜（４）で表される化合物などの芳香族テトラカルボン酸二無水物を挙げることができる。これらは１種単独でまたは２種以上組み合わせて用いられる。

(Wherein R ¹ and R ⁴ represent a divalent organic group having an aromatic ring, R ² and R ³ represent a hydrogen atom or an alkyl group, and a plurality of R ² and R ³ are the same. But it may be different.)
Ethylene glycol-bis (anhydro trimellitate), propylene glycol-bis (anhydro trimellitate), 1,4-butanediol-bis (anhydro trimellitate), 1,6-hexanediol-bis (am Hydrotrimellitate), 1,8-octanediol-bis (anhydrotrimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydrotrimellitate), the following formulas (1) to Aromatic tetracarboxylic dianhydrides such as compounds represented by (4) can be mentioned. These may be used alone or in combination of two or more.

  Examples of the compound represented by the formula (I) include compounds represented by the following formulas (5) to (7), and examples of the compound represented by the formula (II) include the following formula (8). ).

これらは１種単独でまたは２種以上組み合わせて用いられる。

These may be used alone or in combination of two or more.

(solvent)
The organic solvent used for the synthesis of the polyamic acid is not particularly limited as long as it can dissolve the tetracarboxylic dianhydride, the diamine compound, and the polyamic acid generated by the reaction. For example, γ-butyrolactone, N-methyl- Aprotic polar solvents such as 2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetramethylurea, hexamethylphosphoryltriamide, 1,3-dimethyl-2-imidazolidinone; Mention may be made of phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol.
The amount (A) of the organic solvent used is such that the total amount (B) of the tetracarboxylic dianhydride as the reaction raw material and the diamine compound is 0.1 to 30% by weight based on the total amount (A + B) of the reaction solution. It is preferable that the amount is small.
In addition, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination with the organic solvent as long as the resulting polyamic acid does not precipitate. be able to. Specific examples of such poor solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetic acid. Methyl, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monomethyl ester Ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol dimethyl ether , Dipropylene glycol diethyl ether, ethylene glycol ethyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, ethyl lactate, methyl lactate, butyl lactate, ethyl ethoxy acetate, ethyl hydroxy acetate, 2 -Methyl hydroxy-3-methylbutanoate, 3-metho Methyl cypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methyl-3-methoxybutanol, 3-ethyl-3-methoxybutanol, 2-methyl-2-methoxybutanol, 2-ethyl- 2-methoxybutanol, 3-methyl-3-ethoxybutanol, 3-ethyl-3-ethoxybutanol, 2-methyl-2-ethoxybutanol, 2-ethyl-2-ethoxybutanol, tetrahydrofuran, dichloromethane, 1,2-dichloroethane Examples thereof include 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These can be used alone or in combination of two or more.

The imidation reaction conditions usually depend on the glass transition temperature of the resulting polyimide, but the temperature range is from 80 ° C. to 250 ° C., preferably from 100 ° C. to 220 ° C. If it is 80 degrees C or less, there are too many residues of a solvent and a catalyst and it is not preferable.
Processing time is between 5 minutes and 360 minutes. The range is preferably 10 minutes to 240 minutes. If it is 5 minutes or less, there is too much residual solvent or catalyst, which is not preferable.

In the present invention, the polyimide film can be formed by, for example, a casting method in which a solution containing a polyamic acid and a catalyst compound is cast on a substrate by casting, and is formed into a film. Here, the substrate is not particularly limited as long as it is a substrate used in an ordinary solution casting method, and for example, a substrate made of plastic, glass, metal or the like is used.
Moreover, the thickness of the polyimide film to which the present invention can be applied is usually about 5 to 300 μm.

The polyimide film produced as described above can be removed from the catalyst compound and the solvent remaining in the film by immersing in a liquid in which the used catalyst compound and the film-forming solvent are dissolved.
The solution for dissolving the used catalyst compound and the film-forming solvent is not particularly limited as long as it is a solution that dissolves only the used catalyst compound and the film-forming solvent without dissolving the formed polyimide film. Preferably, after removing the catalyst and the film-forming solvent, it is desirable that the polyimide film can be dried at a low temperature of 120 ° C. or lower. For example, water, alcohol solvents such as methanol, ethanol and isopropanol, low-boiling solvents such as acetone and acetonitrile, or aqueous solutions thereof can be used.
When immersing the polyimide film in which the catalyst compound or the film-forming solvent remains, the liquid dissolving the catalyst compound or the film-forming solvent is 10 parts by weight or more, preferably 30 parts by weight or more with respect to 1 part by weight of the polyimide film. It is preferable to have a contact ratio. In order to minimize the amount of residual catalyst compound and solvent in the polyimide film, it is preferable to maintain a contact ratio as large as possible. In addition, it is effective to reduce the remaining amount by exchanging the solution to be immersed or causing the solution to overflow. It is effective to stir the immersed liquid.
The immersion temperature is preferably in the range of 5 ° C to 100 ° C, although it depends on the boiling point of the solution used. If it exceeds 100 ° C., the liquid to be immersed will evaporate, which is not preferable.
The immersion time is usually in the range of 10 minutes to 240 hours, although it depends on the amount of catalyst compound and film-forming solvent remaining, the contact ratio, and the treatment temperature. Preferably, it is in the range of 30 minutes to 100 hours.
After performing the immersion treatment as described above, the polyimide film is taken out and dried at 30 to 120 ° C., preferably 50 to 100 ° C., for 10 to 180 minutes, preferably 15 to 60 minutes to obtain a polyimide film. it can.

Examples Examples of the present invention are shown below.
Measurement method (1) Viscosity measurement ηinh of polyamic acid solution was measured with a Ubbelohde viscometer in a polymer concentration of 0.5 g / dL, 30 ° C. and DMFc. 0.32 dL / gηinh is 0.32 dL / g (concentration 0.5 g / L, 30 ° C., DMFc), 30 ° C., DMFc)
(2) Measurement of imidization rate The film cast on the glass substrate was subjected to heat treatment, and the imidization rate was calculated from the absorption peak ratios of the infrared absorption spectra before and after the diamond ATR method. In the case of a kapton type polyimide obtained from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether, a C—O stretch (b: 1235 cm −1) of the phenyl ether portion not affected by the polyamic acid and the polyimide state Paying attention to the absorption peak intensity of CN stretching (a: 1375 cm −1) generated along with imide ring formation, the imidization rate was determined from the following calculation formula.

Imidation rate (%) = {a / b [sample] a / b [initial]} / {a / b [imide reference] a / b [initial]} × 100

a / b: Absorption peak ratio of 1375 cm −1 / 1235 cm −1
[initial]: Unprocessed sample
[sample]: Heat treatment sample
[Imide reference]: 100% imidized sample heat-treated at 350 ° C. for 6 hours (3) Measurement of residual catalyst amount and residual solvent amount in film The amount of added compound in the film was determined by the TDS (Thermal of the cast film). The measurement was performed by Desorption Spectrometer measurement. The measurement was performed under an initial pressure reduction degree of 1E-10 from room temperature to 300 ° C. under a temperature rising condition of 1 ° C./min, and the presence or absence of the residual catalyst and the residual solvent was confirmed from the mass number signal derived from the compound.

Production synthesis example 1 of polyamic acid
Nitrogen gas is allowed to flow through a vessel equipped with a stirrer and a nitrogen gas introduction tube, and the inside of the vessel is sufficiently replaced with nitrogen gas. After 119 g of N, N-dimethylacetamide (DMAc) is added, 4,4′-diaminodiphenyl ether 10 0.012 g (50 mmol) was added and dissolved sufficiently at room temperature. Then, 10.906 g (50 mmol) of pyromellitic dianhydride was added. The monomer concentration was 15% by weight. The polymerization reaction was stirred at room temperature for 20 hours to obtain a corresponding polyamic acid solution. The resulting polyamic acid had a viscosity ηinh of 0.74 dL / g.

Synthesis example 2
A polyamic acid solution was obtained in the same manner as in Synthesis Example 1, except that 11.209 g (50 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride was used as tetracarboxylic dianhydride. The resulting polyamic acid had a viscosity ηinh of 0.82 dL / g.

Example 1
0.075 g of 1,4-diazabicyclo [2,2,2] octene (Fw = 112.17, 5% by weight with respect to the polymer) in 10 g of the polyamic acid solution (polyamic acid concentration of 15% by weight) prepared in Synthesis Example 1 A polyamic acid solution sufficiently dissolved at room temperature is cast on a glass substrate and a silicon wafer, and heated on a hot plate at 75 ° C. for 1 hour and 100 ° C. for 1 hour. The solvent was removed and heat treatment was performed at 200 ° C. for 1 hour to obtain a polyimide film having a thickness of 50 μm. The obtained film was cut into 10 cm square and immersed in 1 L of water at room temperature for 24 hours, then taken out and dried in a hot air circulation oven at 80 ° C. for 1 hour.
The imidation ratio calculated from the infrared absorption spectrum was 100%. From the TDS measurement, mass number signals derived from 1,4-diazabicyclo [2,2,2] octene and DMAc were not observed.

Example 2
In Example 1, 1,4-diazabicyclo [2,2,2] octene was changed in the same manner as in Example 1 except that the polyamic acid produced in Synthesis Example 2 was used instead of the polyamic acid produced in Synthesis Example 1. Addition and operation were performed to obtain a polyimide film. The obtained film was cut into 10 cm square and immersed in 1 L of water at room temperature for 24 hours, then taken out and dried in a hot air circulation oven at 80 ° C. for 1 hour.
The imidation ratio calculated from the infrared absorption spectrum was 100%. From the TDS measurement, mass number signals derived from 1,4-diazabicyclo [2,2,2] octene and DMAc were not observed.
The obtained polyimide was soluble in organic solvents such as N-methyl-2-pyrrolidone (NMP) and DMAc.

Example 3
Instead of 1,4-diazabicyclo [2,2,2] octene in Example 1, 0.075 g of 1,8-diazabicyclo [5,4,0] -7-undecene (Fw = 152.24, based on polymer) 5 wt%, 0.069 equivalents based on the imide ring that can be formed), and other operations were carried out in the same manner to obtain a polyimide film. The obtained film was cut into 10 cm square and immersed in 1 L of water at room temperature for 24 hours, then taken out and dried in a hot air circulation oven at 80 ° C. for 1 hour.
The imidation ratio calculated from the infrared absorption spectrum was 100%. From the TDS measurement, signals of mass numbers derived from 1,8-diazabicyclo [5,4,0] -7-undecene and DMAc were not observed.

Example 4
In Example 1, instead of 1,4-diazabicyclo [2,2,2] octene, 0.375 g of 4-hydroxypyridine (Fw = 95.10, 0.545 equivalent to the imide ring that can be produced) was added. A polyimide film was obtained in the same manner as in Example 1 except that it was used. The obtained film was cut into 10 cm square and immersed in 1 L of water at room temperature for 24 hours, then taken out and dried in a hot air circulation oven at 80 ° C. for 1 hour.
The imidation ratio calculated from the infrared absorption spectrum was 98%. From the TDS measurement, no mass number signals derived from 4-hydroxypyridine and DMAc were observed. I was not able to admit.

Example 5
A polyimide film was obtained in the same manner as Example 1. The obtained film was cut into 10 cm square and immersed in 1 L of methanol at room temperature for 24 hours, then taken out and dried in a hot air circulation oven at 60 ° C. for 1 hour.
The imidation ratio calculated from the infrared absorption spectrum was 100%. From the TDS measurement, mass number signals derived from 1,4-diazabicyclo [2,2,2] octene and DMAc were not observed.

Example 6
A polyimide film was obtained in the same manner as in Example 4. The obtained film was cut into 10 cm square and immersed in 1 L of 30 wt% methanol aqueous solution at room temperature for 24 hours, then taken out and dried in a hot air circulation oven at 80 ° C. for 1 hour.
The imidation ratio calculated from the infrared absorption spectrum was 100%. From the TDS measurement, no mass number signals derived from 4-hydroxypyridine and DMAc were observed. I was not able to admit.

Comparative Example 1
The polyamic acid solution (polyamic acid concentration 15% by weight) prepared in Example 1 was cast on a glass substrate, the solvent was removed at 75 ° C. for 1 hour and 100 ° C. for 1 hour using a pot plate, and heat treatment was performed at 200 ° C. for 1 hour. Thus, a polyimide film having a thickness of 50 μm was obtained.
The imidation ratio calculated from the infrared absorption spectrum was 100%, but signals of mass numbers derived from 1,4-diazabicyclo [2,2,2] octene and DMAc were observed.

Comparative Example 2
The polyamic acid solution (polyamic acid concentration 15% by weight) prepared in Example 2 was cast on a glass substrate, the solvent was removed at 75 ° C. for 1 hour and 100 ° C. for 1 hour using a pot plate, and heat treated at 200 ° C. for 1 hour. Thus, a polyimide film having a thickness of 50 μm was obtained.
The imidation ratio calculated from the infrared absorption spectrum was 100%, but signals of mass numbers derived from 1,4-diazabicyclo [2,2,2] octene and DMAc were observed.

Comparative Example 3
The polyamic acid solution (polyamic acid concentration 15% by weight) prepared in Example 4 was cast on a glass substrate, the solvent was removed on a hot plate at 75 ° C. for 1 hour, 100 ° C. for 1 hour, and heat treated at 200 ° C. for 1 hour. A polyimide film having a thickness of 50 μm was obtained.
The imidation ratio calculated from the infrared absorption spectrum was 98%. From the TDS measurement, a mass number signal derived from 4-hydroxypyridine and DMAc was observed.

Claims (4)

A film obtained by casting using a solution comprising a polyamic acid having a repeating unit represented by the following general formula (A) and a catalyst compound capable of acid-base interaction with the polyamic acid, and the resulting film, A method for producing a polyimide film, wherein the film is dried after being immersed in a solution in which the catalyst compound and the film-forming solvent in the solution are soluble.

... General formula (A)
{In General Formula (A), X represents a tetravalent organic group, and Y represents a divalent organic group. }   The method for producing a polyimide film according to claim 1, wherein the liquid for immersing the polyimide film is water.   The method for producing a polyimide film according to claim 1, wherein the liquid for immersing the polyimide film comprises an organic solvent in which the obtained polyimide film does not dissolve and the used catalyst compound and the solvent are soluble. The catalyst compound is a group comprising a nitrogen-containing basic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having at least two hydroxyl groups having a molecular weight of 1000 or less, or an aromatic heterocyclic compound. The method for producing a polyimide film according to claim 1, wherein the method is at least one kind of compound selected from the above.