WO2009116500A1 - Polyimide material, polyimide film, method for producing the polyimide material and method for producing the polyimide film - Google Patents

Abstract

Disclosed is a low-cost polyimide film having excellent heat resistance, colorless transparency, formability and optical characteristics. The film contains a polyamic acid and/or a polyimide which is obtained by reacting (A) at least one acyl compound selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic acid, 2,3,5-tricarboxycyclopentylacetic acid dianhydride and reactive derivatives of those, and (B) a specific aromatic imino-forming compound in such a manner that the molar ratio between (A) the acyl compound and (B) the aromatic imino-forming compound is within the range from 1.000:0.960 to 1.000:0.995.

Description

POLYIMIDE MATERIAL, POLYIMIDE FILM AND METHOD FOR PRODUCING THEM

The present invention relates to a polyimide material, a polyimide film, and a method for producing them.

In general, wholly aromatic polyimide obtained from aromatic tetracarboxylic dianhydride and aromatic diamine is due to the rigidity of the molecule, the fact that the molecule is resonance-stabilized, the strong chemical bond, etc. Excellent heat resistance, mechanical properties, electrical properties, oxidation resistance and hydrolysis resistance. Widely used as film, coating agent, molded part, insulation material in fields such as electricity, battery, automobile and aerospace industry. in use. On the other hand, materials used for optical members are required to be excellent in colorless transparency, easy moldability (molding), and optical characteristics in addition to excellent heat resistance and mechanical characteristics. Here, for example, the wholly aromatic polyimide film represented by Kapton (manufactured by Toray DuPont) has excellent heat resistance as described above, and is suitable for the fields of machinery, electricity, etc. In addition, there is a problem in that use as an optical material is limited because of high and low moldability. That is, there is a problem that the film is colored from yellow to brown due to absorption in the visible light region derived from intermolecular or intramolecular charge transfer interaction. In addition, the film has a problem that the process load is high and the moldability is low, for example, heat treatment at a high temperature is required to form the film. Specifically, the polyimide forming the film has low solubility in an organic solvent, and the film cannot be formed using the polyimide as it is. Therefore, using a solution of polyamic acid that is a precursor of the polyimide, and forming a film-like coating film by coating on a substrate, the coating film is heat-treated at a high temperature of about 400 ° C. It is necessary to imidize polyamic acid to obtain a film made of polyimide.

In order to solve such problems, various types of polyimides have been proposed in which non-coloring properties and transparency are improved, and solubility in an organic solvent is imparted to improve moldability. For example, a (fully aromatic) polyimide copolymer having a specific repeating structure having a perfluoroalkyl group has been proposed (Patent Document 1). In addition, a polyimide obtained from cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride and an aromatic diamine such as 4,4′-diaminodiphenyl ether has been proposed (non- Patent Document 1). This polyimide is a semi-aromatic polyimide obtained by using an aromatic and an aliphatic dianhydride in combination. And at least one acyl-containing compound selected from the group consisting of 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, and reactive derivatives thereof; A polyimide resin obtained by reacting an aromatic diamine represented by a specific formula has been proposed (Patent Documents 2 and 3).
Japanese Patent No. 3131940 JP 2006-199945 A JP 2007-326962 A High Performance Polymer 19, P175-193 (2007)

The polyimide copolymer described in Patent Document 1 has excellent heat resistance and improved transparency and solubility in organic solvents, but has problems of low light resistance and high cost. The polyimide described in Non-Patent Document 1 is excellent in heat resistance and has improved transparency as compared with conventional polyimides, but is still insufficient in transparency for use as an optical material. There is. In addition, since this polyimide remains low in solubility in organic solvents, heat treatment (thermal imidation) at a high temperature using a polyamic acid as a precursor is necessary to form it into a film. The problem that the load is large and the moldability is poor remains. Although the polyimide resins described in Patent Documents 2 and 3 have improved transparency, there is a problem that the film is colored initially or over time due to oxidation of the diamine monomer used. In this respect, any film made of a polyimide resin or the like described in the above document has a problem that the non-coloring property is insufficient for use as an optical member. Furthermore, a common problem in the case of using polyimide as the material of the optical member is that the film is colored initially or over time due to oxidation of the diamine monomer used. In this respect, the film made of the polyimide resin or the like described in each of the above documents is insufficient in non-coloring properties for use as an optical member. On the other hand, polyarylate and polycarbonate are listed as materials with excellent optical properties. However, the glass transfer point of these materials is 200 ° C or less, the heat resistance is limited, and solder resistance is not expected. It does not have sufficient performance as a material for a substrate. Polyacrylic acid resins, epoxy resins, and silicon resins have been proposed as materials for optical members other than aromatic polymers, all of which satisfy all of the characteristics required for optical members. It wasn't. Polyacrylic acid resins and epoxy resins have excellent transparency and optical properties, but have a problem of low heat resistance. Particularly in recent years, with the development of light-emitting diodes, solar cells, flat displays, etc., higher brightness and shorter wavelengths of light-emitting devices are progressing, and optical members are exposed to higher temperatures and higher energy. These resins cannot meet such requirements. On the other hand, although silicon resin is excellent in heat resistance, it has low adhesion to other members, and may deteriorate device reliability by peeling from the substrate, etc. Thus, there is a problem that the light extraction efficiency is low. The present invention has been made in view of the above-described problems, and is heat resistant, colorless and transparent (non-coloring and transparency), and moldability (ease when forming into a film and small process load). An object of the present invention is to provide a polyimide material having excellent optical properties and low cost, a composition containing the polyimide material, a polyimide film comprising the polyimide material, and a method for producing the polyimide material and the film. To do.

As a result of intensive studies to solve the above problems, the present inventor obtained a polyamic acid and / or polyimide obtained from a specific acyl compound and a specific aromatic imino-forming compound (diamine and / or diisocyanate). It has been found that the above object of the present invention can be achieved by the polyimide film to be included, and the present invention has been completed.

That is, the present invention provides the following [1] to [14].
[1] (A) 2,3,5-tricarboxycyclopentylacetic acid represented by the following formula (1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride represented by the following formula (2), and Polyamic acid and / or polyimide obtained by reacting at least one acyl compound selected from the group consisting of these reactive derivatives and (B) an aromatic imino-forming compound represented by the following formula (3) A polyimide material characterized by comprising:

(In the formula (3), X is —NH ₂ or —N═C═O, —NHSi (R ²⁵ ) (R ²⁶ ) (R ²⁷ ), Y is a direct bond, —CH ₂ —, —O— , —S—, —C (CH ₃ ) ₂ —, wherein Z is a direct bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ) ₂ —,> C = O, -SO ₂ - is one group selected ^from, R 1 ^{~ R 16} are each independently hydrogen, an alkyl group, a vinyl group, an aryl group, a group selected from ^{halogen, R 25} R ²⁷ is each independently an alkyl group having 1 to 15 carbon atoms.)
[2] The polyimide system according to [1], wherein the aromatic imino-forming compound (B) is a compound formed by bonding all of the bonding groups X, Y, and Z at the para position in the formula (3). material.
[3] The polyimide material according to the above [1] or [2], wherein the polyamic acid and / or the polyimide has a polystyrene equivalent weight average molecular weight of 50,000 to 500,000.
[4] The polyamic acid and / or polyimide has a molar ratio of (A) acyl compound to (B) aromatic imino formation ((A) acyl compound: (B) aromatic imino formation) is 1.000: The polyimide material according to any one of the above [1] to [3], which is obtained by reacting such that 0.960 to 1.000: 0.995.
[5] The polyamic acid and / or the polyimide is an aromatic imino-forming compound, and further the total σ of substituent constants obtained by Hammett's rule (where the total σ is based on the amino group and the substituent constant of the amino group itself) In any one of [1] to [4] above, which is obtained by reacting with an aromatic diamine compound having a value exceeding −0.11 and not more than 2.0. Polyimide material.
[6] A polyimide resin composition comprising the polyimide material according to any one of [1] to [5] above and an organic solvent.
[7] A polyimide film comprising the polyimide material according to any one of [1] to [5].
[8] The polyimide film according to [7], which is for an optical member.
[9] The polyimide film according to [7], which is for a printed wiring board.
[10] (A) 2,3,5-tricarboxycyclopentylacetic acid represented by the following formula (1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride represented by the following formula (2), and At least one acyl compound selected from the group consisting of these reactive derivatives and (B) an aromatic imino-forming compound represented by the following formula (3) are reacted in an organic solvent to give a polyamic acid. A method for producing a polyimide-based material, comprising a step of obtaining and imidizing at least a part of the polyamic acid.

(In the formula (3), X is —NH ₂ or —N═C═O, —NHSi (R ²⁵ ) (R ²⁶ ) (R ²⁷ ), Y is a direct bond, —CH ₂ —, —O— , —S—, —C (CH ₃ ) ₂ —, wherein Z is a direct bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ) ₂ —,> C = O, -SO ₂ - is one group selected ^from, R 1 ^{~ R 16} are each independently hydrogen, an alkyl group, a vinyl group, an aryl group, a group selected from ^{halogen, R 25} ~ ^{R 27} are each independently an alkyl group having 1 to 15 carbon atoms.)
[11] The method for producing a polyimide material according to [10], wherein at least a part of the polyamic acid is imidized in the presence of an alicyclic tertiary monoamine.
[12] The method for producing a polyimide material according to [11], wherein the alicyclic tertiary monoamine is a compound represented by the following formula (6).

(In the formula (6), R is an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom or sulfur atom, l is 0 or 1, and m and n are each independently an integer of 0 to 2. .)
[13] Furthermore, at least one dehydrating agent selected from the group consisting of acetic anhydride, propionic anhydride, benzoic anhydride, acid chlorides corresponding to these anhydrides, and carbodiimide compounds The method for producing a polyimide material according to the above [11] or [12], wherein
[14] A step of applying a solution containing the polyimide material obtained by the method according to any one of [10] to [13] above and an organic solvent on a substrate to form a coating film; And a step of removing the organic solvent by evaporating and removing the film from the film to obtain a film.

The polyimide material comprising the polyamic acid and / or polyimide (hereinafter also referred to as “polyimide etc.”) of the present invention is composed of a polyamic acid and / or polyimide obtained from a specific acyl compound and an aromatic imino forming compound. Excellent heat resistance and transparency, little coloring (yellowing) and low cost. In the present invention, since the polyimide obtained from the specific component has excellent solubility in an organic solvent, it can be dissolved in an organic solvent as it is to form a film. In this case, after applying a solution containing the polyimide or the like and an organic solvent to a substrate or the like to form a coating film, it may be heated at a temperature at which the solvent in the coating film evaporates. Since it is not necessary to perform heat treatment at a high temperature exceeding 400 ° C. as in the case of thermal imidization using a solution containing the same, a reduction in process load can be achieved. The polyimide material of the present invention and the polyimide film containing the polyimide material can be used for light emitting diode peripheral materials, solar cell peripheral materials, flat display peripheral materials, and electronic circuit peripheral materials. Specifically, it can be used as an optical member such as a heat-resistant transparent film and a conductive transparent film. Examples of the flat display peripheral material include substrates for transparent flexible displays such as liquid crystal displays, plasma displays, organic electroluminescence displays, and electronic paper. Examples of the electronic circuit peripheral material include a printed wiring board forming material and a printed wiring board. Specifically, the flexible printed wiring board, the rigid printed wiring board, the optoelectronic printed wiring board, the COF (Chip on Film) substrate, TAB (Tape Automated Bonding) substrate and the like.

1 is a diagram showing an IR spectrum of a polymer obtained in Example 1. FIG. 2 is a graph showing an IR spectrum of the polymer obtained in Example 2. FIG. FIG. 4 is a diagram showing an IR spectrum of the polymer obtained in Example 3. FIG. 6 is a graph showing an IR spectrum of the polymer obtained in Example 4. FIG. 6 is a graph showing an IR spectrum of the polymer obtained in Example 6. 6 is a graph showing an IR spectrum of the polymer obtained in Example 7. FIG. 6 is a diagram showing an IR spectrum of the polymer obtained in Example 8. FIG. FIG. 6 is a graph showing an IR spectrum of the polymer obtained in Example 9. 6 is a diagram showing an IR spectrum of the polymer obtained in Example 10. FIG. FIG. 6 is a graph showing an IR spectrum of the polymer obtained in Example 11. 6 is a graph showing an IR spectrum of the polymer obtained in Example 12. FIG. 2 is a graph showing an IR spectrum of the polymer obtained in Comparative Example 1. FIG. 6 is a diagram showing an IR spectrum of a polymer obtained in Comparative Example 2. FIG.

The polyimide material of the present invention comprises a polyamic acid and / or polyimide obtained from (A) a specific acyl compound and (B) a specific imino forming compound. First, (A) component and (B) component are demonstrated. [Component (A)] The component (A) includes 2,3,5-tricarboxycyclopentylacetic acid represented by the following formula (1), 2,3,5-tricarboxycyclopentyl represented by the following formula (2) It is at least one acyl compound selected from the group consisting of acetic dianhydride and reactive derivatives thereof. By using such an acyl compound, a polyimide having excellent solubility in an organic solvent can be obtained, and a film having high heat resistance and little coloring can be obtained.

Examples of the reactive derivative include 2,3,5-tricarboxycyclopentylacetic acid monomethyl ester, 2,3,5-tricarboxycyclopentylacetic acid dimethyl ester, 2,3,5-tricarboxycyclopentylacetic acid trimethyl ester, 5-tricarboxycyclopentyl acetic acid tetramethyl ester, 2,3,5-tricarboxycyclopentyl acetic acid monoethyl ester, 2,3,5-tricarboxycyclopentyl acetic acid diethyl ester, 2,3,5-tricarboxycyclopentyl acetic acid triethyl ester, Examples include 2,3,5-tricarboxycyclopentylacetic acid tetraethyl ester, and esterified products in which the above alkyl ester is replaced with unsubstituted phenyl ester or various para-substituted phenyl esters.Other reactive derivatives include acid chlorides such as 2,3,5-tricarboxycyclopentylacetic acid tetrachloride and 2,3,5-tricarboxycyclopentylacetic acid dichloride diester (the alcohol or phenol component of the ester is the same as above). Can be mentioned. As the component (A), 2,3,5-tricarboxycyclopentylacetic acid dianhydride is preferably used. When 2,3,5-tricarboxycyclopentylacetic acid dianhydride, which is an anhydride, is used as component (A), a polyamic acid can be synthesized at a lower temperature than when a non-anhydride is used. These acyl compounds can be used alone or in combination of two or more.

[Component (B)] The component (B) includes an aromatic imino forming compound represented by the following formula (3) as the component (B-1).

(In the formula (3), X is -NH ₂ or ^{-N = C = O, -NHSi (} R 25) (R 26) (R 27), Y is a direct bond (single bond), - CH ₂ - , —O—, —S—, —C (CH ₃ ) ₂ —, wherein Z is a direct bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ). ₂ —,> C═O, —SO ₂ —, wherein R ¹ to R ¹⁶ are each independently a group selected from a hydrogen atom, an alkyl group, a vinyl group, an aryl group, and a halogen. R ²⁵ to R ²⁷ are each independently an alkyl group having 1 to 15 carbon atoms.) An aromatic imino-forming compound having four benzene rings represented by such a specific formula By using it, a film with little coloring can be obtained. Here, the “imino forming compound” refers to a compound for reacting with the component (A) to form imino.

Examples of the aromatic imino-forming compound include bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and bis [4- (3-aminophenoxy) phenyl] ketone. Bis [4- (4-aminophenoxy) phenyl] ketone, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3- Aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 2 , 2-bis [4- (3-amino-α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (4- Amino-α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (3-isocyanato-α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (4-isocyanato-) α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (3-trimethylsilylamino-α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (4-trimethylsilylamino-) α, α-dimethylbenzyl) phenyl] propane and the like. Of these, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-Amino-α, α-dimethylbenzyl) phenyl] propane and 2,2-bis [4- (4-amino-α, α-dimethylbenzyl) phenyl] propane are preferably used.

As the component (B-1), an aromatic imino-forming compound in which the bonding groups represented by X, Y, and Z in the above formula (3) are bonded at the para position, that is, the following formula (4) Aromatic imino-forming compounds represented by By using such a compound, a film having higher heat resistance and less coloring can be obtained. Among the above-mentioned aromatic imino forming compounds, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-amino) Phenoxy) phenyl] propane and 2,2-bis [4- (4-amino-α, α-dimethylbenzyl) phenyl] propane are more preferably used.

(In the formula ^{(4), R 1 ~ R} 16, X, Y, and Z are the same as in the formula (3).)

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

In addition to the compound represented by the above formula (3) (component (B-1)) as an aromatic imino-forming compound, the polyimide-based material of the present invention has a total σ of substituent constants obtained by Hammett's rule (where, The total σ is based on the amino group and does not include the substituent constant of the amino group itself. The aromatic diamine compound ((B -2) Component) can be used. The aromatic diamine compound is preferably an aromatic diamine compound having σ exceeding −0.11 and not more than 1.6, more preferably σ exceeding −0.11 and 0 It is an aromatic diamine compound within the range of .8 or less.
In this case, as the component (B-1), the total σ of substituent constants obtained by Hammett's rule (however, the total σ is based on the amino group and does not include the substituent constant of the amino group itself). ) Is in the range of −0.70 or more and −0.11 or less.
The difference in total σ between the component (B-1) and the component (B-2) is preferably 0.1 or more, more preferably 0.2 or more. Preferable examples of the component (B-2) include aromatic diamine compounds represented by the following formula (5).

(In the formula (5), X represents —NH ₂ , Y represents a direct bond,> C═O, —SO ₂ —, one group selected from —C (CF ₃ ) ₂ —, and R ¹⁷ to R ²⁴ is each independently a group selected from a hydrogen atom, an alkyl group, a fluorinated alkyl group, an alkoxy group, a vinyl group, an aryl group, and a halogen.)

Preferred examples of the component (B-2) include 2,2′-bis (trifluoromethyl) benzidine, 2,2′-dimethoxybenzidine, 2,2′-dimethylbenzidine, 3,3′-diaminodiphenylsulfone, Selected from the group consisting of 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, and 1,1,1,3,3,3-hexafluoroisopropylidenebisaniline The at least 1 type of aromatic diamine compound is mentioned. Particularly preferred examples include 2,2'-bis (trifluoromethyl) benzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylsulfone, and 4,4'-diaminodiphenylsulfone. Component (B-2) can be used alone or in combination of two or more.

Next, a method for producing the polyimide of the present invention will be described. The method for producing a polyimide-based material of the present invention comprises (a) a step of reacting the (A) acyl compound and the (B) aromatic imino forming compound in an organic solvent to obtain a polyamic acid, and (b) And imidating at least a part of the polyamic acid.

[Step (a)] Step (a) is a step of obtaining a polyamic acid by reacting the component (A) and the component (B) in an organic solvent. As a specific method for reacting the component (A) and the component (B), at least one (B) aromatic imino-forming compound is dissolved in an organic solvent, and then at least 1 is added to the resulting solution. Examples include a method in which a seed (A) acyl compound is added and stirred at a temperature of 0 to 100 ° C. for 1 to 60 hours. Examples of the organic solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, N, N′-dimethylimidazolidinone, and tetramethyl. Aprotic polar solvents such as urea; phenolic solvents such as cresol, xylenol, and halogenated phenol; Of these, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are preferable. These solvents can be used alone or in combination of two or more. The total amount of the aromatic imino forming compound and the acyl compound in the reaction solution is preferably 5 to 30% by mass of the total amount of the reaction solution. The ratio of (A) acyl compound to (B) aromatic imino-forming compound is such that 1 equivalent of the amino group or isocyanate group of component (B) and 0.8 to 1.1 of the acid anhydride group of component (A). A ratio of 2 equivalents is preferable, and a ratio of 1.0 to 1.1 equivalents is more preferable. More specifically, the reaction can be performed such that the molar ratio of (A) acyl compound to (B) aromatic imino forming compound is 1.000: 0.960 to 1.000: 0.995. The reaction is preferably performed to be 1.000: 0.970 to 1.000: 0.990. When the molar ratio of the (A) acyl compound and the (B) aromatic imino forming compound is within the above range, the polymer formed is particularly excellent in film formability, mechanical properties, and transparency. When the component (B-1) and the component (B-2) are used as the aromatic imino-forming compound (B), the molar ratio of the component (B-1) to the component (B-2) is (B- It is preferable that 1) / (B-2)> 1. The molar ratio of (B-1) :( B-2) is more preferably 0.60: 0.40 to 0.999: 0.001, more preferably 0.62 when the total is 1. : 0.38 to 0.99: 0.01, particularly preferably 0.65: 0.35 to 0.96: 0.04. When the amount of the component (B-2) is within the above range with respect to 1 mol of the total of the component (B-1) and the component (B-2), the film formability and mechanical properties of the resulting film Excellent properties and transparency. The polyamic acid refers to an acid having a structure containing —CO—NH— and —CO—OH, which is generated by a reaction between an acid anhydride group and an amino group, or a derivative thereof (specifically, For example, CO—NH— and —CO—OR (where R is an alkyl group or the like) are used. The polyamic acid becomes a polyimide having a cyclic chemical structure (—CO—N—CO—) by dehydration of —CO—NH—H and —CO—OH OH by heating or the like.

[Step (b)] Step (b) is a step of obtaining a solution containing polyimide and an organic solvent by imidizing at least a part of the polyamic acid obtained in the step (a) by dehydration ring closure. is there. Specific imidization methods include a method using a dehydrating agent (chemical imidization), and a heat treatment method at 160 ° C. to 350 ° C. (about 160 to 220 ° C. for a solution, generally 300 ° C. or more for a cast film). (Thermal imidization). Examples of the dehydrating agent in chemical imidization include acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, or corresponding acid chlorides, carbodiimide compounds such as dicyclohexylcarbodiimide, and the like. The addition amount of the dehydrating agent can be appropriately changed according to the target imidization rate, but is usually in the range of 1 to 10 mol and in the range of 2 to 10 mol with respect to 1 mol of the acyl compound. Is preferred.
The chemical imidization can be performed at a temperature of 10 ° C. to 120 ° C., and is preferably performed at a temperature of 25 ° C. to 90 ° C. When the temperature exceeds 120 ° C., coloring may not be suppressed. When the temperature is lower than 10 ° C., the reaction rate is low and imidization may take time.
In the case of thermal imidization, it is preferable to carry out while removing water generated by the dehydration reaction out of the system. At this time, water can be removed azeotropically using benzene, toluene, xylene or the like.
As the imidization method, chemical imidization is preferable because imidization can be performed by heating at a lower temperature.
In the imidization, a base catalyst such as pyridine, isoquinoline, trimethylamine, triethylamine, N, N-dimethylaminopyridine, imidazole or alicyclic tertiary monoamine can be used as necessary. Among these, alicyclic tertiary monoamines are preferably used. When an alicyclic tertiary monoamine compound is used for imidization, the imidization reaction is promoted because the lone pair of electrons on the nitrogen atom of the alicyclic tertiary monoamine has high nucleophilicity. It is done.
As said alicyclic tertiary monoamine, the compound represented by following formula (6) is used suitably.

(In general formula (6), R is an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom or sulfur atom, l is 0 or 1, and m and n are each independently an integer of 0 to 2. .)
In formula (6), R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. M and n are preferably 0 or 1. Further, m + n is preferably 1 to 3.
Preferable examples of the compound represented by the above formula (6) include N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine and the like.

By using an alicyclic tertiary monoamine as an imidization catalyst, even if an aliphatic compound is used as the component (A), it can be imidized with high reactivity (imidation reaction rate), and at a lower temperature. Imidization and shortening of the time required for imidization can be achieved. As a result, it is possible to reduce the coloring of the resulting polyimide. In addition, when a compound having a particularly difficult imidization, such as a compound having a 6-membered ring anhydride skeleton or a compound in which at least two carbons constituting a crosslinked ring structure form an anhydride skeleton, is used as the component (A). It is possible to achieve a high imidization rate that could not be achieved conventionally even under low temperature conditions.
The base catalyst is preferably used in an amount of 0.01 to 10 mol, particularly preferably 0.1 to 5 mol, per mol of the acyl compound. The imidization is performed so as to imidize at least a part of the polyamic acid, preferably 75 mol% or more, more preferably 85 mol% or more, and particularly preferably 90 mol% or more. The obtained polyamic acid and / or a solution containing polyimide and an organic solvent can be used as it is, but after isolating polyimide or the like as a solid component, it can also be used by re-dissolving in an organic solvent. In addition, as an organic solvent which redissolves, the thing similar to the said organic solvent is mentioned. As a method for isolating polyimide and the like, a solution containing polyimide and an organic solvent is poured into a poor solvent for polyimide such as methanol to precipitate the polyimide and the like, and the polyimide and the like are separated as a solid content by filtration, washing, drying, and the like. The method of doing is mentioned. By performing such an operation, it is possible to remove the dehydration catalyst (imidization catalyst) used in the imidization.

The obtained polyamic acid and / or polyimide has a polystyrene-equivalent weight average molecular weight of 50,000 to 500,000, preferably 100,000 to 400,000. In the present invention, the ratio of polyimide in the total 100 mol% of polyamic acid and polyimide is 75 mol% or more, preferably 85 mol% or more, particularly preferably 90 mol% or more. If the proportion of polyimide is less than 75 mol%, the water absorption rate of the film may increase or the durability may decrease.

Next, the method for producing the film of the present invention will be described. The method for producing a film of the present invention comprises a solution containing a polyamic acid and / or polyimide obtained by reacting the (A) acyl compound and the (B) aromatic imino-forming compound and an organic solvent on a substrate. A step (c) of forming a coating film by applying to the layer and a step (d) of obtaining a film by removing the organic solvent from the coating layer by evaporating. [Step (c)] Step (c) is a step of forming a coating film by applying a solution containing the polyimide and the like and an organic solvent onto a substrate. Examples of the substrate include a polyethylene terephthalate (PET) film, a SUS plate, and a copper foil. As a method for applying a solution containing polyimide or the like and an organic solvent on the substrate, a roll coating method, a gravure coating method, a spin coating method, a method using a doctor blade, or the like can be used. The thickness of the coating film is not particularly limited, but is, for example, 1 to 250 μm.

[Step (d)] Step (d) is a step of removing the organic solvent from the coating film by evaporation to obtain a film. Specifically, the organic solvent in the coating film is evaporated and removed by heating the coating film. The heating conditions are not particularly limited as long as the organic solvent evaporates. For example, the heating conditions are 60 to 250 ° C. for 1 to 5 hours. Heating may be performed in two stages. For example, after heating at 100 ° C. for 30 minutes, heating at 150 ° C. for 1 hour. Further, if necessary, drying may be performed under a nitrogen atmosphere or under reduced pressure. In this step, it is sufficient if the organic solvent can be removed, and it is not necessary to perform imidization. Therefore, a film can be obtained at a lower temperature than in the conventional technique. Therefore, even if other members forming the optical member have low heat resistance, the film is removed by directly applying a solution containing the polyimide or the like and an organic solvent to the member and evaporating and removing the organic solvent. Can be formed. The obtained film can be used as it is without being peeled off from the support substrate.

The film of the present invention mainly comprises a polyimide obtained by reacting the component (A) and the component (B). Here, the polyamic acid formed by reacting the component (A) and the component (B) has, for example, at least one repeating unit represented by the following formulas (7) to (10).

(In the formulas (7) to (10), R ¹ to R ¹⁶ , X, Y and Z are the same as in the above formula (3), and R ¹⁷ to R ²⁴ are each independently a hydrogen atom. Or represents an alkyl group. Furthermore, the polyimide formed by the reaction of the component (A) and the component (B) has, for example, a repeating unit represented by the following formula (11) or (12).

(In the formula (11), R ¹ to R ¹⁶ , X, Y, and Z are the same as in the above formula (3).)

(In the formula (12), R ¹ to R ¹⁶ , X, Y, and Z are the same as those in the above formula (3).)

In the film of the present invention, the thickness is 1 to 250 μm, preferably 5 to 200 μm. Further, when the film of the present invention is used as a substrate, it is particularly preferably 10 to 150 μm. The film of the present invention has a total light transmittance of preferably 80% or more, more preferably 85% or more, and further preferably 89% or more when the thickness is 20 μm. When the film of the present invention has a thickness of 20 μm, the YI value (yellow index) is preferably 2.5 or less, and more preferably 1.4 or less. The film of the present invention preferably has a refractive index of 1.58 to 1.66, more preferably 1.60 to 1.64 with respect to light having a wavelength of 633 nm. The film of the present invention has a glass transition temperature (Tg) of preferably 250 ° C. or higher, and more preferably 280 ° C. or higher. By having such a glass transition temperature, excellent heat resistance can be obtained. The film of the present invention preferably has a tensile strength of 80 MPa to 300 MPa, more preferably 100 MPa to 300 MPa. The film of the present invention preferably has a tensile elongation of 10% to 200%, more preferably 20% to 150%. The film of the present invention preferably has a tensile elastic modulus of 2.2 GPa or more, more preferably 2.5 GPa or more.

The film of the present invention can be used for light emitting diode peripheral materials, solar cell peripheral materials, flat display peripheral materials, and electronic circuit peripheral materials. Specifically, it can be used for optical members such as heat-resistant transparent films and conductive transparent films. Examples of the flat display peripheral material include substrates for transparent flexible displays such as liquid crystal displays, plasma displays, organic electroluminescence displays, and electronic paper. Moreover, as an electronic circuit peripheral material, it can also be used as a printed wiring board substrate, a flexible printed wiring board, a rigid printed wiring board, an optoelectronic printed wiring board, a COF (Chip on Film) board, a TAB ( A substrate for Tape Automated Bonding) can be given. When used as a printed wiring board, for example, a copper layer for wiring can be provided. Examples of the method for producing a printed wiring board in which a copper layer is provided on a film include a casting method, a laminating method, and a metalizing method. The casting method can be achieved, for example, by using a copper foil as the substrate used in the step (b). Specifically, after a solution containing polyimide and an organic solvent is applied on a copper foil to form a coating film, the organic solvent is removed from the coating film to provide a copper layer on the film. A wiring board can be manufactured. As a method of providing a copper layer on the film of the present invention, in the case of a laminating method, for example, a printed wiring provided with a copper layer by hot pressing a copper foil on the film of the present invention obtained by the laminating method. Substrates can be manufactured. In the case of the laminating method, for example, a printed wiring board provided with a copper layer can be produced by hot pressing a copper foil on the film of the present invention. In the case of the metalizing method, for example, after the surface modification is performed in order to develop the affinity of the film of the present invention with the metal, the Ni-based metal layer bonded to the polyimide by vapor deposition or sputtering is used. A seed layer necessary for wet electroplating is formed. And the board | substrate for printed wiring with which the copper layer was provided can be manufactured by providing the copper layer of a predetermined film thickness with a wet-plating method.

Moreover, the polyimide-type solution containing the polyimide etc. and organic solvent obtained by process (a), (b) is a light emitting diode peripheral material, a solar cell peripheral material, a flat display peripheral material, an electron as a polyimide-type resin composition. It can also be used as a circuit peripheral material. Specifically, it can be used as a sealant, a lens material, a printed wiring board forming material, and the like. For example, when used as a printed wiring board forming material, a printed wiring board can be manufactured by a casting method. Specifically, a printed wiring board provided with a copper layer can be produced by applying a heat treatment after applying the polyimide resin composition on a copper foil.
In addition, the said polyimide resin composition can use the organic solvent whose boiling point is 150 degrees C or less as a cosolvent. Examples of the organic solvent include methanol, ethanol, isopropanol, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane and the like.
These solvents can be used alone or in combination of two or more.
The concentration of polyamic acid and / or polyimide in the polyimide resin composition is preferably 5 to 30% by mass of the total amount of the reaction solution.

Hereinafter, the present invention will be specifically described by way of examples. Example 1 First, 9.88 g (22.8 mmol) of bis [4- (3-aminophenoxy) phenyl] sulfone was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. ) Was added. Next, after the atmosphere in the flask was replaced with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (60 ml) was added and stirred until uniform. To the resulting solution, 5.12 g (22.8 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride was added at room temperature, and the reaction was continued for 12 hours at the same temperature to give a solution containing polyamic acid. Obtained. NMP (75 ml) was added to the resulting polyamic acid-containing solution for dilution, pyridine (7.4 ml) and acetic anhydride (6.5 ml) were added, and the mixture was stirred at 110 ° C. for 6 hours for imidization. A polymer was obtained. Then, after cooling to room temperature, it poured into a lot of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 13.4 g, yield 94.5%). Subsequently, the obtained polymer was redissolved in N, N-dimethylacetamide (DMAc) to obtain a 20% by mass resin solution. The resin solution is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. It peeled. Thereafter, the film was further dried at 150 ° C. under reduced pressure for 3 hours to obtain a film having a thickness of 20 μm. About the said polymer, the structural analysis, the weight average molecular weight, and the imidation ratio were measured by the following method. As a result, the characteristic absorption of the carbonyl group was 1739 cm ⁻¹ and 1698 cm ⁻¹ (see FIG. 1), and the weight average molecular weight was 174,000. The imidization ratio of the polymer obtained (the ratio of the amic acid that was dehydrated and cyclized among all the amic acid) was 93%. Moreover, the solubility with respect to the organic solvent of a polymer, the total light transmittance of a film, YI value, a refractive index, a glass transition point, and the YI value after a heat test were evaluated by the following method. The results are shown in Table 1. (1) Structural analysis It was performed by IR (KBr method). (2) Weight average molecular weight The weight average molecular weight was measured using an HLC-8020 GPC apparatus manufactured by TOSOH. As the solvent, N-methyl-2-pyrrolidone (NMP) to which lithium bromide and phosphoric acid were added was used, and the molecular weight in terms of polystyrene was determined at a measurement temperature of 40 ° C. (3) Ring closure rate (imidization rate) The ring closure rate of polyimide was measured using 1H-NMR. D-DMSO was used as a solvent. The ring closure rate was calculated from the ratio of the peak integral value of the amide in the amic acid part (9.8 to 10.3 ppm) and the peak integral value of the aromatic diamine (6.5 to 7.5 ppm). (4) Solubility in Organic Solvent The polymer was dissolved in N, N-dimethylacetamide and adjusted to a 20% by mass solution, and the solubility at room temperature was evaluated. The case where it was completely dissolved was indicated as “◯”, and the case where there was a swollen or insoluble polymer was indicated as “x”. (5) Total light transmittance, measured according to YI JIS K7105 transparency test method. Specifically, the total light transmittance and YI value (yellow index) of the film were measured using an SC-3H haze meter manufactured by Suga Test Instruments Co., Ltd. (6) Refractive index The refractive index of the obtained film at a wavelength of 633 nm was measured using a 2010 type prism coupler manufactured by Metricon. The measurement was performed using a silicon wafer substrate at 23 ° C. and 50% RH. (7) Glass transition temperature (Tg) The glass transition temperature (Tg) was measured using a Rigaku 8230 type DSC measuring apparatus at a rate of temperature rise of 20 ° C / min. (8) YI value after heat resistance test The obtained film (50 cm square) was placed in a hot air drier maintained at 150 ° C. for 24 hours, and a heat resistance acceleration test was performed. The YI value of the film after the test was measured by the same method as in (5) above. (9) Tensile properties The mechanical strength of the obtained film was measured in accordance with JIS K7127 for room temperature tensile strength, tensile elongation, and tensile modulus.

Example 2 A white powder was obtained in the same manner as in Example 1 except that bis [4- (4-aminophenoxy) phenyl] sulfone was used instead of bis [4- (3-aminophenoxy) phenyl] sulfone. Polymer (yield 13.8 g, yield 97.3%) and a film were obtained. With respect to the obtained polymer, structural analysis, weight average molecular weight, and imidation rate were measured in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1739 cm ⁻¹ and 1696 cm ⁻¹ (see FIG. 2), and the weight average molecular weight was 339,000. The imidation ratio of the obtained polymer was 94%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 3] Instead of bis [4- (3-aminophenoxy) phenyl] sulfone, 9.33 g (25.3 mmol) of bis (4-aminophenoxy) biphenyl was used, and 2,3,5-tricarboxycyclopentylacetic acid was used. A white powder was obtained in the same manner as in Example 1 except that the amounts of dianhydride, pyridine, and acetic anhydride were changed to 5.67 g, (25.3 mmol), 8.2 ml, and 7.2 ml, respectively. Polymer (yield 13.2 g, yield 94.0%) and a film were obtained. With respect to the obtained polymer, structural analysis, weight average molecular weight, and imidation rate were measured in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1738 cm ⁻¹ and 1695 cm ⁻¹ (see FIG. 3), and the weight average molecular weight was 292,000. The imidation ratio of the obtained polymer was 93%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 4] In place of bis [4- (3-aminophenoxy) phenyl] sulfone, 9.70 g (23.6 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was used. Except that the blending amounts of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, pyridine, and acetic anhydride were changed to 5.30 g (23.6 mmol), 7.5 ml, and 6.7 ml, respectively. In the same manner as in Example 1, a white powder polymer (yield 13.5 g, yield 95.3%) and a film were obtained. With respect to the obtained polymer, structural analysis, weight average molecular weight, and imidation rate were measured in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1735 cm ⁻¹ and 1682 cm ⁻¹ (see FIG. 4), and the weight average molecular weight was 320,000. The imidation ratio of the obtained polymer was 93%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 5] After preparing polyamic acid in the same manner as in Example 4, NMP (75 ml) was added to dilute, xylene (12 ml) and isoquinoline (1 drop; 7 ml) were added, and the mixture was stirred at 180 ° C for 6 hours. Then, imidization was performed to obtain a polymer. Thereafter, the polymer was isolated in the same manner as in Example 1 to obtain a white powder (yield 13.2 g, yield 93.3%). Using the obtained polymer, a film was obtained in the same manner as in Example 1. For the obtained polymer, the weight average molecular weight and the imidization ratio were measured in the same manner as in Example 1. As a result, the weight average molecular weight was 190,000 and the imidization ratio was 89%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 6]
First, bis [4- (4-aminophenoxy) phenyl] sulfone (9.75 g, 22.54 mmol) was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube. . Next, after the atmosphere in the flask was replaced with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (60 ml) was added and stirred until uniform. To the resulting solution was added 2,3,5-tricarboxycyclopentylacetic acid dianhydride (5.12 g, 22.84 mmol; anhydride: amine = 1: 0.987) at room temperature and stirred at that temperature for 12 hours. Were reacted to obtain a solution containing polyamic acid. NMP (75 ml) was added to the resulting polyamic acid-containing solution for dilution, pyridine (7.4 ml) and acetic anhydride (6.5 ml) were added, and the mixture was stirred at 110 ° C. for 6 hours for imidization. A polymer was obtained. Then, after cooling to room temperature, it poured into a lot of methanol, and the polymer was isolated by filtration. The resulting polymer was vacuum dried at 60 ° C. overnight to give a white powder (13.4 g, 95.0%). Subsequently, the obtained polymer was redissolved in N, N-dimethylacetamide (DMAc) to obtain a 20% by mass resin solution. The resin solution is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. It peeled. Thereafter, the film was further dried at 150 ° C. under reduced pressure for 3 hours to obtain a film having a thickness of 20 μm.
With respect to the obtained polymer, structural analysis, weight average molecular weight, and imidation rate were measured in the same manner as in Example 1. Results, characteristic absorption of carbonyl group, 1740 cm ^-1 and 1,695 cm ^-1 (imide group), 1892cm ^-1 (end group) (see FIG. 5), the weight average molecular weight was 149,000.
The imidation ratio of the obtained polymer (ratio of the amic acid subjected to dehydration and ring closure in the total amic acid) was 94%.
Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 7]
Except that the amount of bis [4- (4-aminophenoxy) phenyl] sulfone was changed to 9.51 g (21.99 mmol; anhydride: amine = 1: 0.963), the same as in Example 6, A white powder polymer (yield 13.1 g, yield 94.6%) and a film were obtained.
With respect to the obtained polymer, structural analysis, weight average molecular weight, and imidation rate were measured in the same manner as in Example 1. Results, characteristic absorption of carbonyl group, 1740 cm ^-1 and 1,695 cm ^-1 (imide group), 1892cm ^-1 (end group) (see FIG. 6), the number of repeating units is 55, the weight average molecular weight of at 66,000 there were.
The imidation ratio of the obtained polymer was 93%.
Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 8]
Instead of bis [4- (4-aminophenoxy) phenyl] sulfone, 9.58 g (23.34 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane; anhydride: amine = 1: 0 .987) was used in the same manner as in Example 1 to obtain a white powder polymer (13.3 g, yield 95.0%) and a film.
With respect to the obtained polymer, structural analysis, weight average molecular weight, and imidation rate were measured in the same manner as in Example 1. Results, characteristic absorption of carbonyl group, 1737cm ^-1 and 1680 cm ^-1 (imide group), 1892cm ^-1 (end group) (see FIG. 7), the number of repeating units 160, weight average molecular weight, in 183,000 there were.
The imidation ratio of the obtained polymer was 95%.
Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Example 9] First, in a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, and a cooling tube, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (9. 24 g, 22.5 mmol; (B-1) component) and 2,2′-bis (trifluoromethyl) benzidine (0.38 g, 1.2 mmol; (B-2) component) were added. Next, after the atmosphere in the flask was replaced with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (135 g) was added and stirred until uniform. 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (5.38 g, 24.0 mmol; component (A)) was added to the resulting solution at room temperature, and the reaction was continued for 24 hours at the same temperature. A solution containing polyamic acid was obtained. N-methylpiperidine (2.7 ml) and acetic anhydride (6.7 ml) were added to the resulting solution containing polyamic acid, and the mixture was stirred at 75 ° C. for 3 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 13.1 g, yield 93%). Subsequently, the obtained polymer was redissolved in N, N-dimethylacetamide (DMAc) to obtain a 20% by mass resin solution. The resin solution is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. It peeled. Thereafter, the film was further dried at 150 ° C. under reduced pressure for 3 hours to obtain a film having a thickness of 20 μm.
About the obtained polymer, the measurement of the weight average molecular weight and imidation ratio was performed by the method similar to Example 1. FIG. The weight average molecular weight of the obtained polymer was 104,000, and the imidization ratio (ratio of the amic acid that was dehydrated and cyclized among all amic acids) was 95%.
The obtained film was subjected to structural analysis by IR (ATR method: film). The results show that the characteristic absorption of the carbonyl group is 1735 cm ⁻¹ and 1684 cm ⁻¹ (see FIG. 8), the solubility of the polymer in the organic solvent, the total light transmittance of the film, the YI value, and the glass transition point. Evaluation was performed in the same manner as in 1. As for the YI value after the heat test, the obtained film (5 cm square) was placed in a hot air drier held at 175 ° C. for 12 hours to conduct a heat resistance acceleration test, and the YI value of the film after the heat test was calculated. It measured by the method similar to said (5). The results are shown in Table 1.

Example 10 9.36 g (22.8 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as the component (B-1) and 2,2 ′ as the component (B-2) -Example 9 except that 0.26 g (1.2 mmol) of dimethylbenzidine and 5.38 g (24.0 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride were used as the component (A). Similarly, a polymer composed of white powder (yield 13.2 g, yield 94%) and a film were obtained. The obtained polymer was subjected to structural analysis, weight average molecular weight and imidization rate measurement in the same manner as in Example 9. Results, characteristic absorption of carbonyl group, a 1736 cm ^-1 and 1683cm ^-1 (see FIG. 9), the weight average molecular weight of 183,000, the imidization ratio was 97%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 9. The results are shown in Table 1.

[Example 11] 9.32 g (22.7 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as the component (B-1) and 2,2 ′ as the component (B-2) -Example 9 except that 0.25 g (1.2 mmol) of dimethylbenzidine and 5.43 g (24.2 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride were used as component (A). Similarly, a polymer composed of white powder (yield 13.2 g, yield 94%) and a film were obtained. The obtained polymer was subjected to structural analysis, weight average molecular weight and imidization rate measurement in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1735 cm ⁻¹ and 1683 cm ⁻¹ (see FIG. 10), the weight average molecular weight was 138,000, and the imidization ratio was 93%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 9. The results are shown in Table 1.

Example 12 9.19 g (22.4 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane as the component (B-1) and 2,2 ′ as the component (B-2) -Example 9 except that 0.25 g (1.2 mmol) of dimethylbenzidine and 5.56 g (24.8 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride were used as component (A). Similarly, a polymer composed of white powder (yield 12.8 g, yield 91%) and a film were obtained. The obtained polymer was subjected to structural analysis, weight average molecular weight and imidization rate measurement in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1735 cm ⁻¹ and 1684 cm ⁻¹ (see FIG. 11), the weight average molecular weight was 52,000, and the imidization ratio was 95%. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 9. The results are shown in Table 1.

[Example 13]
2,2-bis [4- (4-aminophenoxy) phenyl] propane (6.47 g, 15.8 mmol) was added to a 300 mL four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and condenser. Next, after the atmosphere in the flask was replaced with nitrogen, N-methyl-2-pyrrolidone (hereinafter referred to as NMP) (90.0 g) was added and stirred until uniform. 2,3,5-Tricarboxycyclopentylacetic acid dianhydride (3.53 g, 15.8 mmol) was added to the resulting solution at room temperature, and stirring was continued at that temperature for 24 hours to obtain a polyamic acid solution.
Next, N-methylpiperidine (1.9 ml) and acetic anhydride (4.5 ml) were added to the obtained polyamic acid solution, and the mixture was stirred at 75 ° C. for 4 hours for imidization. After cooling to room temperature, it was poured into a large amount of methanol, and the polymer was isolated by filtration. The obtained polymer was vacuum-dried overnight at 60 ° C. to obtain a white powder (yield 9.20 g, yield 97.5% by mass).
Subsequently, the obtained polymer was redissolved in N, N-dimethylacetamide (DMAc) to obtain a 20% by mass resin solution. Then, the resin solution was applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes and further at 150 ° C. for 60 minutes, and then peeled off from the PET substrate. Thereafter, the film was further dried at 180 ° C. under reduced pressure for 8 hours to obtain a film having a thickness of 20 μm.
The ring closure rate (imidation rate) of the polymer and the weight average molecular weight of the polyamic acid and the polymer (polymer after imidization) were evaluated in the same manner as in Example 1. The imidation ratio of the obtained polymer was 98%. Moreover, the weight average molecular weight of the polyamic acid was 4.0 × 10 ⁵ , and the weight average molecular weight of the obtained polymer (polymer after imidization) was 5.2 × 10 ⁵ .
The total light transmittance and YI value (initial) of the film were evaluated by the same method as in Example 1. Further, the YI value (after UV resistance test) and water absorption were evaluated by the following methods. As for the YI value after the heat test, the obtained film (5 cm square) was put in a hot air drier held at 150 ° C. for 100 hours to conduct a heat resistance acceleration test, and the YI value of the film after the heat test was calculated. It measured by the method similar to said (5). The results are shown in Table 1.
(10) YI value after UV resistance test The obtained film (5 cm square) is placed in a QUV tester (accelerated weather resistance tester) using UV fluorescent lamp UVA-351 as a light source for one week, and UV accelerated test Went. The YI value of the film after the test was measured by the same method as in (5) above.
(11) Water absorption test Three pieces of the obtained film were cut into a size of 3 cm × 4 cm and dried at 180 ° C. for 8 hours under reduced pressure drying. After measuring the mass of the film, the film was immersed in distilled water at 25 ° C. for 24 hours. After immersion, water droplets on the film surface were wiped off, and the water absorption (mass%) was calculated from the mass change before and after immersion.
The calculation formula of the water absorption rate is as follows.
Water absorption rate (%) = {[(mass after soaking) ÷ (mass before soaking)]-1} × 100

[Example 14]
A polymer composed of a white powder (yield 9.20 g, yield 97.5 mass%) and a film were obtained in the same manner as in Example 1 except that the temperature of the imidization reaction was 40 ° C. and the reaction time was 48 hours. .
The ring closure rate (imidation rate) and weight average molecular weight of the obtained polymer were evaluated in the same manner as in Example 1. The imidation ratio of the obtained polymer was 95%. Moreover, the weight average molecular weight of the polyamic acid was 4.0 × 10 ⁵ , and the weight average molecular weight of the obtained polymer (polymer after imidization) was 5.6 × 10 ⁵ .
Further, the total light transmittance, YI value (initial, after heat resistance test, after UV resistance test), and water absorption of the film were evaluated in the same manner as in Example 13. The results are shown in Table 1.

[Comparative Example 1] Instead of bis [4- (3-aminophenoxy) phenyl] sulfone, 7.08 g (35.3 mmol) of 4,4'-diaminodiphenyl ether was used, and 2,3,5-tricarboxycyclopentyl acetate A light brown powder was prepared in the same manner as in Example 1 except that the amounts of anhydride, pyridine, and acetic anhydride were changed to 7.92 g (35.3 mmol), 11.4 ml, and 10.0 ml, respectively. A polymer (yield 12.7 g, yield 92.7%) and a film were obtained. The obtained polymer was subjected to structural analysis and weight average molecular weight measurement in the same manner as in Example 1. Results, characteristic absorption of carbonyl group, 1739Cm there ^-1 and 1689cm ^-1 (see FIG. 12), the weight average molecular weight was 295,000. The imidation ratio of the obtained polymer was 92%. The imidization ratio was calculated from the ratio of amic acid NH signal and aromatic ring hydrogen signal ratio in 1H-NMR. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 2] Instead of 2,3,5-tricarboxycyclopentylacetic acid dianhydride used in Example 4, 4.88 g (24.6 mmol) of butanetetracarboxylic dianhydride was used. Except that the amounts of bis [4- (4-aminophenoxy) phenyl] propane, pyridine, and acetic anhydride were changed to 10.12 g (24.6 mmol), 8.0 ml, and 7.0 ml, respectively. In the same manner as in Example 4, a white powder polymer (yield 13.3 g, yield 94.0%) and a film were obtained. The obtained polymer was subjected to structural analysis and weight average molecular weight measurement in the same manner as in Example 1. As a result, the characteristic absorption of the carbonyl group was 1781 cm ⁻¹ and 1705 cm ⁻¹ (see FIG. 13), and the weight average molecular weight was 120,000. The imidation ratio of the obtained polymer was 96%. The imidization ratio was calculated from the ratio of amic acid NH signal and aromatic ring hydrogen signal ratio in 1H-NMR. Further, various physical properties of the obtained polymer and film were evaluated in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 3] Instead of 2,3,5-tricarboxycyclopentylacetic acid dianhydride used in Example 4, 4.85 g (24.7 mmol) of cyclobutanetetracarboxylic dianhydride was used. Except that the amounts of bis [4- (4-aminophenoxy) phenyl] propane, pyridine, and acetic anhydride were changed to 10.15 g (24.7 mmol), 8.0 ml, and 7.0 ml, respectively. A polymer was prepared in the same manner as in Example 4, but no further structural analysis was performed because the polymer precipitated during imidization.

From Table 1, according to the present invention, since polyimide has excellent solubility in organic solvents, a film can be formed without heat treatment at a high temperature (for example, about 400 ° C.) (excellent moldability). In addition, the obtained film has a high total light transmittance (transparency), a low YI value (yellowness) even after a heat test, a high refractive index, a high Tg and a high heat resistance. It turns out that it is excellent. From Examples 6 to 8 in Table 1, according to the present invention, polyimides and the like synthesized with specific monomers at specific molar ratios have high total light transmittance (transparency), high Tg, and excellent heat resistance. It can be seen that even after the heat resistance test, the YI value (yellowness) is low and the coloration is very excellent. Further, from Examples 9 to 12 in Table 1, according to the present invention, (A) a specific acyl compound and (B) a specific aromatic diamine compound (two types of aromatic diamine compounds having different reactivities) Since the polyimide and the like that are reacted have excellent solubility in an organic solvent, a film can be formed without heat treatment at a high temperature (for example, about 400 ° C.) (with excellent moldability) In addition, the obtained film has a high total light transmittance (transparency), a high Tg and excellent heat resistance, and the YI value even after the heat resistance test at a temperature higher than those of Examples 1 to 8. It can be seen that (yellowness) is low and the non-coloring property is very excellent. In particular, polyimide or the like obtained by reacting the component (A) and the component (B) at a specific molar ratio (and the molar ratio of the component (B-1) to the component (B-2) is within a specific range. In some polyimides and the like, excellent results are obtained in heat resistance and YI after a heat test. Also, from Examples 13 and 14 in Table 1, it can be seen that according to the present invention, since a specific catalyst is used, imidization can be performed at a lower temperature than in the prior art. Moreover, since the obtained polyimide has the outstanding solubility with respect to the organic solvent, it can form a film, without heat-processing at high temperature (for example, about 400 degreeC). Further, from Table 1, the films of the present invention (Examples 1 to 4) have high transparency (total light transmittance), and there is little yellowing immediately after film formation and after UV resistance test, Furthermore, it turns out that a water absorption is low. Furthermore, it can be seen that the YI value (yellowness) is low and the non-coloring property is very excellent even after the heat resistance test for a longer time than in Examples 1 to 8. On the other hand, it can be seen that Comparative Example 1 using 4,4'-diaminodiphenyl ether instead of the component (B) has a high YI value both immediately after film formation and after the heat resistance test, and is not suitable for an optical member. In Comparative Example 3 using cyclobutanetetracarboxylic dianhydride instead of component (A), the solubility of polyimide in an organic solvent is low, and polyimide cannot be deposited in the solvent to form a film. I understand. In Comparative Example 2, although a film can be formed, it can be seen that the obtained film has a low Tg and is inferior in heat resistance.

Claims (14)

1. (A) 2,3,5-tricarboxycyclopentylacetic acid represented by the following formula (1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride represented by the following formula (2), and reaction thereof At least one acyl compound selected from the group consisting of functional derivatives;
   (B) an aromatic imino-forming compound represented by the following formula (3);
   A polyimide-based material comprising a polyamic acid and / or a polyimide obtained by reacting.
   

   

   

   

   (In the formula (3), X is —NH ₂ or —N═C═O, —NHSi (R ²⁵ ) (R ²⁶ ) (R ²⁷ ), Y is a direct bond, —CH ₂ —, —O— , —S—, —C (CH ₃ ) ₂ —, wherein Z is a direct bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ) ₂ —,> C = O, -SO ₂ - is one group selected ^from, R 1 ^{~ R 16} are each independently hydrogen, an alkyl group, a vinyl group, an aryl group, a group selected from ^{halogen, R 25} R ²⁷ is each independently an alkyl group having 1 to 15 carbon atoms.)
2. The polyimide-based material according to claim 1, wherein the (B) aromatic imino-forming compound is a compound in which the bonding groups X, Y, and Z are all bonded at the para position in the above formula (3).
3. The polyimide material according to claim 1 or 2, wherein the polyamic acid and / or the polyimide has a polystyrene equivalent weight average molecular weight of 50,000 to 500,000.
4. The polyamic acid and / or polyimide has a molar ratio of (A) acyl compound to (B) aromatic imino formation ((A) acyl compound: (B) aromatic imino formation) is 1.000: 0.960. The polyimide-based material according to any one of claims 1 to 3, which is obtained by reacting so as to have a ratio of -1.000: 0.995.
5. Polyamic acid and / or polyimide, as an aromatic imino-forming compound, is further the total σ of substituent constants obtained by Hammett's rule (however, the total σ is based on the amino group and does not include the substituent constant of the amino group itself) The polyimide-based material according to any one of claims 1 to 4, wherein the polyimide-based material is obtained by reacting with an aromatic diamine compound that exceeds -0.11 and is not more than 2.0. .
6. A polyimide resin composition comprising the polyimide material according to any one of claims 1 to 5 and an organic solvent.
7. A polyimide film comprising the polyimide material according to any one of claims 1 to 5.
8. The polyimide film according to claim 7, which is used for an optical member.
9. The polyimide film according to claim 7, which is for a printed wiring board.
10. (A) 2,3,5-tricarboxycyclopentylacetic acid represented by the following formula (1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride represented by the following formula (2), and reaction thereof At least one acyl compound selected from the group consisting of functional derivatives;
    (B) an aromatic imino-forming compound represented by the following formula (3);
    A process for obtaining a polyamic acid by reacting in an organic solvent, and a process for imidizing at least a part of the polyamic acid.
    

    

    

    (In the formula (3), X is —NH ₂ or —N═C═O, —NHSi (R ²⁵ ) (R ²⁶ ) (R ²⁷ ), Y is a direct bond, —CH ₂ —, —O— , —S—, —C (CH ₃ ) ₂ —, wherein Z is a direct bond, —CH ₂ —, —O—, —S—, —C (CH ₃ ) ₂ —,> C = O, -SO ₂ - is one group selected ^from, R 1 ^{~ R 16} are each independently hydrogen, an alkyl group, a vinyl group, an aryl group, a group selected from ^{halogen, R 25} R ²⁷ is each independently an alkyl group having 1 to 15 carbon atoms.)
11. The method for producing a polyimide-based material according to claim 10, wherein at least a part of the polyamic acid is imidized in the presence of an alicyclic tertiary monoamine.
12. The method for producing a polyimide-based material according to claim 11, wherein the alicyclic tertiary monoamine is a compound represented by the following formula (6).
    

    

    (In the formula (6), R is an alkyl group having 1 to 4 carbon atoms, X is an oxygen atom or sulfur atom, l is 0 or 1, and m and n are each independently an integer of 0 to 2. .)
13. Further, claim using at least one dehydrating agent selected from the group consisting of acetic anhydride, propionic anhydride, benzoic anhydride, acid chlorides corresponding to these anhydrides, and carbodiimide compounds Item 13. The method for producing a polyimide material according to Item 11 or 12.
14. A step of applying a solution containing the polyimide-based material obtained by the method according to any one of claims 10 to 13 and an organic solvent on a substrate to form a coating film, and the organic solvent is removed from the coating film. A method for producing a polyimide film, comprising: removing by evaporation to obtain a polyimide film.

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