TW201400527A - High-transparency polyimide resin - Google Patents

Abstract

The present invention provides a polyimide resin having high transparency, excellent heat resistance, and a low coefficient of linear thermal expansion, and pertains more specifically to a polyimide resin obtained by running an imidization polymerization reaction of bicyclo[4.2.0]octane-3,4,7,8-tetracarboxylic dianhydride, an aromatic diamine compound, and, as needed, an alicyclic diamine compound, the total of the diamine compounds being in the range of 90-110 in terms of molar ratio in relation to 100 of the tetracarboxylic dianhydride.

Description

Highly transparent polyimide resin Field of invention

This invention relates to highly transparent polyimine resins.

Background of the invention

Conventionally, since the polyimide resin is excellent in heat resistance, strength, electrical insulation, and the like, it is often used as a resin for electronic materials. However, general polyimine resins have limitations in use due to their strong coloration.

Here, there has been a study on the improvement of the hue of the polyimine resin, and a method of using a fluorine compound on the raw material of the polyimide resin has been found (Non-Patent Document 1). However, since the raw material of the polyimine resin having a fluorine atom is difficult to manufacture and expensive, it is not economical.

There are also studies in which an aliphatic or alicyclic compound is used as a raw material for the improvement of the hue of the polyimide resin in the polyimide resin raw material. In particular, when an alicyclic acid dihydrate is used, it has been found to have a large effect on the improvement of hue (Non-Patent Document 2).

Further, transparent polyimides are expected to be used in place of glass in particular. In the field of flat panel display, the mainstream is the method of using a glass substrate. Although the glass is excellent in properties such as high transparency, high heat resistance, and low coefficient of linear expansion, it is easily broken when it is washed, and there is a ratio. A major problem. Therefore, it has been sought to develop a polyimide resin which is excellent in flexibility which satisfies high transparency, high heat resistance, and low linear expansion coefficient.

[Advanced technical literature] [Non-patent literature]

[Non-Patent Document 1] "The latest trends in leaping polyimine IV - Types of versatile ‧ Characteristics ‧ Continuity of processing and use - Release 11th Anniversary Special Edition" issued in March 2008 SB RESEARCH CO. , LTD. P.39

[Non-Patent Document 2] "Latest Polyimine ~ Foundation and Application ~" January 28, 2002, the first edition of the first brush release editor, the Japan Polyimide Research Association, edited by Imai Shuo, Yokota Riko, publisher Yoshida Takashi NTS (shares) P.241~242

Summary of invention

The present invention is intended to provide a polyimide resin which is excellent in high transparency, heat resistance and low linear expansion coefficient.

The inventors of the present invention conducted a review to solve the above problems, and as a result, found that high specificity, heat resistance, and low line can be obtained by using a specific tetracarboxylic dianhydride and a specific diamine compound in a raw material. The polyimine resin which is excellent in the expansion coefficient, and the results of the review are further reviewed to complete the present invention.

That is, the present invention relates to a polyimine resin described below.

Item 1. A polyimine resin which is a tetracarboxylic dianhydride represented by the formula (1) and an aromatic diamine compound, in terms of a molar ratio, relative to the tetracarboxylic dianhydride 100, The total of the amine compounds is obtained by carrying out a ruthenium iodide polymerization in the range of 90 to 110:

The polyimine resin according to Item 1, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chemical 2]

Item 3. The polyimine resin according to Item 1, wherein the aromatic diamine compound is: (A) bis[4-(4-aminophenoxy)phenyl]sulfonic acid, and (B) (3) at least one of the compounds represented by the diamine compound: [Chemical 3]

Item 4. A polyimine resin, which is a tetracarboxylic dianhydride, an aromatic diamine compound, and an alicyclic diamine compound represented by the formula (1), in terms of a molar ratio, relative to the tetracarboxylic acid The acid dianhydride 100, the total of the diamine compounds is obtained by carrying out a ruthenium iodide polymerization in the range of 90 to 110. The formula (1) [Chemical 4]

Item 5. The polyimine resin according to Item 4, wherein the alicyclic diamine compound is at least one of the compounds represented by the diamine compound of the formula (4):

Item 6. The polyimine resin according to Item 4 or 5, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chem. 6]

Item 7. The polyimine resin according to Item 4 or 5, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (5): [Chem. 7]

Item 8. The polyimine resin according to Item 4 or 5, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (6): [Chem. 8]

Item 9. A polyaminic acid resin which is a tetracarboxylic dianhydride represented by the formula (1) and an aromatic diamine compound, in terms of a molar ratio, relative to the tetracarboxylic dianhydride 100, The total of the amine compounds is obtained by copolymerization in the range of 90 to 110:

The polyaminic acid resin according to Item 9, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2):

Item 11. The polyaminic acid resin according to Item 10, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (5): [Chem. 11]

Item 12. A poly-proline resin which is a tetracarboxylic dianhydride, an aromatic diamine compound, and an alicyclic diamine compound represented by the formula (1) in terms of a molar ratio with respect to the tetracarboxylic acid Acid dianhydride 100, the total of the diamine compounds is obtained by performing ruthenium iodide polymerization in the range of 90 to 110: [Chemical 12]

The polyamino acid resin according to Item 12, wherein the alicyclic diamine compound is at least one of the compounds represented by the diamine compound in the formula (4):

The polyamino acid resin according to Item 12 or 13, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chem. 14]

Item 15. A polyimine varnish comprising the polyimine resin according to any one of items 3 to 8 and an organic solvent.

Item 16. A polyamic acid varnish comprising the polyphthalic acid resin according to any one of items 9 to 14 and an organic solvent.

Item 17. A polyimine imide molded article obtained by molding the polyimine varnish described in Item 15.

Item 18. A polyimine shaped article, which is the polyamid varnish according to Item 16. Obtained by forming.

The polyimine imide molded article according to Item 17 or 18, wherein the polyimine imide molded article has a film form, a film form or a sheet form.

Item 20. A plastic substrate comprising the polyimine molded article according to any one of items 17 to 19.

Item 21. An electrical component or an electronic component, comprising the plastic substrate of item 20.

According to the present invention, a polyimide resin having excellent transparency, heat resistance and low coefficient of linear expansion can be obtained. The plastic substrate composed of the molded body of the polyimide resin can be used for electrical parts, electronic parts, and the like.

Further, the polyimide resin can also be used for a heat-resistant insulating material, a heat-resistant coating, a heat-resistant coating material or a heat-resistant adhesive material.

[Formation for implementing the invention]

Hereinafter, the present invention will be described in detail.

I. Polyimine resin

The polyimine resin of the present invention is obtained by carrying out a hydrazine imidization polymerization reaction of a tetracarboxylic dianhydride represented by the following general formula (1) and an aromatic diamine compound;

Alternatively, it is obtained by carrying out a ruthenium iodide polymerization reaction of a tetracarboxylic dianhydride, an aromatic diamine compound and an alicyclic diamine compound represented by the following general formula (1):

I-1. Tetracarboxylic dianhydride represented by the general formula (1)

The tetracarboxylic dianhydride represented by the above formula (1) is a constituent component of the polyimine resin of the present invention and is a bicyclo[4.2.0]octane-3,4,7,8-tetracarboxylic dianhydride. .

The method for producing a tetracarboxylic dianhydride represented by the formula (1) is recommended as a photo-dualization reaction. Specific examples include a molar amount of 1,2,3,6-tetrahydrophthalic anhydride and maleic anhydride dissolved in a ketone solvent such as methyl ethyl ketone, an ester solvent such as ethyl acetate or the like. An ether solvent such as an alkane is irradiated with light of 250 to 400 nm using a high pressure mercury lamp to obtain the tetracarboxylic dianhydride reactant.

The tetracarboxylic dianhydride represented by the formula (1) may be a mono-, di-, tri- or tetra-p-chloride of a tetracarboxylic acid or a tetracarboxylic acid, and a single, double or triple of a lower alcohol having a carbon number of 1 to 4. Or a derivative such as a tetraester.

Further, in the present invention, one portion of the tetracarboxylic dianhydride represented by the formula (1) may be used in combination with other tetracarboxylic dianhydrides insofar as the effects are not impaired. Examples of the other tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride.

Specific examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-diphenylsulfonytetracarboxylic dianhydride, and 4,4'-oxygen. Diphthalic acid dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2-double (3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenoxyphenyl) Propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,2-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-double (3,4-dicarboxyphenyl)ethane dianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, Bis(3,4-dicarboxyphenyl)methane dianhydride, 4,4'-(p-phenylenedioxy)dicarboxylic dianhydride, 4,4'-(m-phenylene dioxygen) Dialkyl phthalic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2-extended ethyl bis (dehydration partial Trimellitic acid), 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-dioxaoxy-3-furan)naphthalene[1,2-c]furan-1.3-two Ketones and their derivatives.

Specific examples of the alicyclic tetracarboxylic dianhydride include 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclobutanetetracarboxylic dianhydride. 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentane Acetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxaoxytetrahydrofuranyl )-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]-octyl-7-ene-2,3,5,6-tetracarboxylic dianhydride And its derivatives and the like.

Specific examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like. Things and so on.

Other tetracarboxylic dianhydrides other than the above may be supplied to the ruthenium iodide polymerization reaction by being appropriately mixed alone or in combination of two or more.

When a part of the tetracarboxylic dianhydride represented by the formula (1) is partially substituted with the above other tetracarboxylic dianhydride, the amount thereof is used in the molar amount relative to the total tetracarboxylic dianhydride, preferably It is 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

I-2. Aromatic diamine compound

The aromatic diamine compound which is a constituent component of the polyimine resin of the present invention is not particularly limited, and a commercially available product or a known production method can be used.

Specific examples of the aromatic diamine compound are, specifically, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4 , 4'-diaminodiphenylanthracene, 3,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 4,4'-diaminodiphenyl sulfide , 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, 1,3- Bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4 -aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy) Phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, bis[4-(4-amine Phenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis (4 -amino-3-chlorophenyl)indole, 9,9-bis(4-amino-3-fluorophenyl)indole, O-tolidine, m-tolidine, 4,4'- Aminobenzamide, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4-aminophenyl 4-aminobenzoate, 2-(4-amine Phenyl)-6-aminobenzobenzene Oxazole and the like. Among them, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diamino group are exemplified. Diphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylanthracene, 3,3'-diaminodiphenylanthracene, 1,4-double ( 4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,3-bis(3- Aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2-bis[4-(3-aminophenoxy)phenyl]propane, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminobenzene Oxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, and the like. These aromatic diamine compounds may be used singly or in combination of two or more kinds as appropriate.

A preferred example of the aromatic diamine compound is an aromatic diamine compound represented by the following formula (2).

[化17]

A more preferred aromatic diamine compound is an aromatic diamine compound represented by the following formula (5).

[化18]

A more preferred aromatic diamine compound is an aromatic diamine compound represented by the following formula (6).

[Chemistry 19]

Further, the aromatic diamine compound is preferably (A) bis[4-(4-aminophenoxy)phenyl]anthracene, and (B) is selected from the group consisting of the following formula (3). At least one of the amine compounds is used in combination.

[Chemistry 20]

More preferably, (A) bis[4-(4-aminophenoxy)phenyl]anthracene and (B) are at least one selected from the group consisting of diamine compounds represented by the following formula (7). And use it.

[Chem. 21]

I-3. alicyclic diamine compound

The alicyclic diamine compound which is a constituent component of the polyimine resin of the present invention can be used without particular limitation, and it can be obtained by using a commercially available product or by a known production method.

Specific examples of the alicyclic diamine compound include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, and tetramethyl-diaminodicyclohexylmethane. Diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(amine Methyl)tricyclo[5.2.1.0 ^2,6 ]decane, 1,3-diaminomethylcyclohexane, isophoronediamine, and the like. These alicyclic diamine compounds may be supplied to the ruthenium iodide polymerization reaction by singly or in combination of two or more kinds as appropriate.

A preferred alicyclic diamine compound is exemplified by a diamine compound represented by the following formula (4).

[化22]

When the alicyclic diamine compound is used in combination with the aromatic diamine compound, the molar ratio of the alicyclic diamine compound to the aromatic diamine compound is in the range of 80 to 20:20 to 80, preferably 75. ~30:25~70 range. Especially 70~40:30~60 is better.

When the alicyclic diamine compound is used in combination with the aromatic diamine compound, the aromatic diamine compound represented by the following formula (2) is exemplified as a preferred aromatic diamine compound.

[化23]

A more preferred aromatic diamine compound is an aromatic diamine compound represented by the following formula (5).

[Chem. 24]

A more preferred aromatic diamine compound is an aromatic diamine compound represented by the following formula (6).

[化25]

Further, the alicyclic diamine compound and/or the aromatic diamine compound may be partially substituted with an aliphatic diamine compound to be used within a range not inhibiting the effects of the present invention.

Specific examples of the aliphatic diamine compound include, for example, ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, and the like.

The above-mentioned aliphatic diamine compound may be supplied to the ruthenium iodide polymerization reaction by being appropriately mixed alone or in combination of two or more.

When a part of the alicyclic diamine compound and/or the aromatic diamine compound is partially substituted with the above aliphatic diamine compound, the amount thereof is preferably 20 in comparison with the molar number of the whole diamine compound. The molar percentage is below, more preferably 10% by mole or less, and particularly preferably less than 5% by mole.

In the present invention, the molar ratio of the imidization polymerization is preferably in the range of from 90 to 110 with respect to all of the tetracarboxylic dianhydride 100. More preferably in the range of 95~105, especially in 98~102 Within the scope. By carrying out the ruthenium iodide polymerization in the range, a polyimine resin having a sufficient degree of polymerization can be obtained. Further, as described above, the tetracarboxylic dianhydride, the alicyclic diamine compound and the aromatic diamine compound may be substituted into an aliphatic diamine compound in a range that can achieve the effects of the invention. In this case, the same molar ratio is also applied.

In the present specification and the scope of the patent application, although the diamine compound is described in the form of a "diamine", it may be converted into a part or all of an amine group for the purpose of increasing the reactivity and achieving the effect of the invention. The isocyanate-based compound or the thiolated compound is substituted for these diamines.

II. Polyurethane resin

The polyphthalic acid resin which is the precursor of the polyimine resin of the present invention is a copolymerization reaction of the above-mentioned tetracarboxylic dianhydride and the diamine compound in a temperature range of 5 ° C to 100 ° C in a reaction solvent. Winner.

II-1. Copolymerization

The reaction solvent used in the above copolymerization reaction may be any solvent which can dissolve the polyamine resin formed by the copolymerization reaction. For example, an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent or the like can be exemplified as a preferred example.

Specific examples of the aprotic solvent are N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam , 1,3-dimethyltetrahydroimidazolidinone, guanamine solvent such as tetramethyl urea, γ-butyrolactone, γ-valerolactone, etc. lactone solvent, hexamethylphosphonium amide, six Phosphorus-containing guanamine solvent such as trimethylamine phosphate, dimethyl hydrazine, dimethyl a sulfur-containing solvent such as ketone, cyclohexane or the like, a ketone solvent such as acetone, cyclohexane or methylcyclohexanone, an amine solvent such as methylpyridine or pyridine, or acetic acid (2-methoxy-1-methyl) An ester solvent such as ethyl).

Specific examples of the phenolic solvent are phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2 , 6-xylenol, 3,4-xylenol, 3,5-xylenol, and the like.

Specific examples of the ether solvent are ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 1,4-two Alkane, etc.

Specific examples of the carbonate-based solvent are diethyl carbonate, methyl ethyl carbonate, ethyl ethyl carbonate, propyl carbonate, and the like.

The above reaction solvents may be used singly or in combination of two or more kinds.

Even in these reaction solvents, special preference is given to N-methyl-2-pyrrolidone, 1,3-dimethyltetrahydroimidazolone. Methyl, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone.

The amount of the reaction solvent used may be any amount as long as it can dissolve the polyamic acid resin formed. The concentration of the specific polyaminic acid resin is preferably adjusted to 5 to 50% by weight, more preferably 10 to 40% by weight, still more preferably 10 to 30% by weight.

In the copolymerization reaction system, from the viewpoint of color prevention and safety of the reaction system, it is preferable to have a gas atmosphere without active gas. Usually, the method of awarding is to replace the reaction system with a non-active gas, so that there is no active gas in the flow reaction. The non-active gas is exemplified by nitrogen, argon, and the like.

Furthermore, for the copolymerization of the poly-proline resin in the present invention It should be possible to use an alkali generating inhibitor. The alkali generating inhibitor is preferably one which can be volatilized and removed when the oxime imidized polyamido resin varnish is heated.

As the above-mentioned base generating inhibitor, for example, a general decylating agent can be used. in particular. N,O-bis(trimethyldecyl)acetamide or N,O-bis(trimethyldecyl)trifluoroacetamide or trimethyldecane chloride or hexamethyldioxane.

The reaction time of the copolymerization reaction of the polyaminic acid resin differs depending on the addition ratio, the substrate concentration, and the like, and is usually preferably from 2 to 24 hours. If the reaction time is too short, it is considered to have a tendency to have a low degree of polymerization. When the reaction time is too long, the degree of polymerization is lowered due to the hydrolysis reaction of a part of the guanamine group.

The obtained polyaminic acid resin preferably has a number average molecular weight of 6,000 or more and a weight average molecular weight of 10,000 or more, more preferably a number average molecular weight of 6,000 to 100,000 and a weight average molecular weight of 10,000 to 500,000. This range is a range of degrees of polymerization having a degree to which a shaped body can be specifically formed. Further, in the present specification and the patent application, the molecular weight of the polyproline resin is a value measured by the method described in the examples below.

II-2. Ruthenium amination polymerization

The method for the polymerization of hydrazine imidization is (1) heating the tetracarboxylic dianhydride and the diamine compound in the presence of a reaction solvent and a small amount of an azeotropic solvent, and distilling the generated water into the heat outside the system by azeotropy. The imidization method, (2) after producing the polyaminic acid precursor of the polyimine precursor, an anhydride such as acetic anhydride or propionic anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide is used. A chemical hydrazine imidation method for performing dehydration, (3) a hydrazine imidization method or the like which is heated to 300 ° C or higher after being produced as a poly phthalic acid precursor of a polyamidene precursor.

II-2-1. In the case where an alicyclic diamine compound is not used in combination as a diamine compound

When the alicyclic diamine compound is not used in combination as the diamine compound, the method for producing the above polyimine resin is industrially preferred (3), and is, for example, 300. The polyaminic acid resin is heated in a temperature range of ~350 ° C, and the produced water accompanying the hydrazine imidization reaction is distilled off to carry out a hydrazine imidization polymerization reaction.

The ruthenium imidization ratio in the heating oxime imidization reaction of the poly (proamino) resin of the above (3) is usually 70% or more, preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. . Furthermore, depending on the use of the polyimide resin, it is also possible to achieve a near-100% ruthenium amination rate.

II-2-2. In the case of using an alicyclic diamine compound as a diamine compound

In the case of using the alicyclic diamine compound as the diamine compound, the method for producing the above polyimine resin is industrially preferred (1), and the following method can be exemplified. : dissolving the entire amount of the tetracarboxylic dianhydride and the diamine compound in the reaction solvent, or heating the portion to 40 to 250 after partially dissolving one of the tetracarboxylic dianhydride and/or the diamine compound. The °C, more preferably 150 to 200 ° C, utilizes an azeotropic solvent to distill off the water formed in the system and thereby carry out the hydrazine imidization polymerization.

Further, with respect to the tetracarboxylic dianhydride, the polydiimide compound can be used to make the terminal of the polyimine resin polymer an amine terminal, and on the other hand, by using tetracarboxylic dianhydride, it is more than the diamine compound. Can make The polymer end of the obtained polyimine resin is an acid end.

The azeotropic solvent used for distilling the above-mentioned produced water from the reaction system may, for example, be an aromatic hydrocarbon such as toluene, xylene or solvent petroleum brain, or a fat such as cyclohexane, methylcyclohexane or dimethylcyclohexane. Cyclic hydrocarbons and the like, which may be used singly or in a mixed system. The amount thereof to be used is usually from 1 to 30% by weight, preferably from about 5 to 10% by weight, based on the amount of the reaction solvent.

In the reaction system, from the viewpoint of prevention of color formation and safety of the reaction system, it is preferred to carry out the reaction under a gas atmosphere without active gas. It is generally recommended to replace the reaction system with an inert gas without using an active gas, so that a reactive gas is not circulated in the reaction. The non-active gas is exemplified by nitrogen, argon, and the like.

In the imidization polymerization in the present invention, a known catalyst can be used. However, the subsequent treatment becomes cumbersome, and the use of a trace amount of the catalyst causes deterioration in the storage stability of the polyimide varnish and coloring of the polyimide varnish, and thus, the reaction is carried out without a catalyst. It is better.

When a catalyst is used, for example, a base catalyst can be used as pyridine, quinoline, isoquinoline, α-methylpyridine, β-methylpyridine, 2,4-dimethylpyridine, 2,6-di. Organic base catalysts such as methylpyridine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline, etc. An inorganic base catalyst represented by potassium or sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate or sodium hydrogencarbonate.

Further, the acid catalyst can be exemplified by crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methyl benzoic acid, oxo-benzoic acid, terephthalic acid, benzenesulfonic acid, P-toluenesulfonic acid

The reaction time of the hydrazine imidization polymerization varies depending on the ratio of addition, the concentration of the substrate, and the like, and after the produced water starts to be distilled off, it is usually preferably from 2 to 10 hours. If the reaction time is too short, it is considered that there is a tendency that the imidization ratio is low. If the reaction time is too long, a partial geothermal bridging reaction occurs, and the reaction system is thickened or forms a gel-like by-product, and the reaction system is colored due to thermal deterioration of the reaction solvent.

The polyimine resin of the present invention obtained by hydrazine imidization polymerization preferably has a number average molecular weight of 6,000 or more, and a weight average molecular weight of 10,000 or more, more preferably a number average molecular weight of 6,000 to 100,000 and a weight. The average molecular weight is in the range of 10,000 to 500,000. This range is a range of degrees of polymerization which is particularly capable of forming a shaped body. Further, in the present specification and the patent application, the molecular weight of the polyimine resin is a value measured by the method described in the examples below.

The oxime imidization ratio in the above hydrazine imidization polymerization reaction is usually 70% or more, preferably 80% or more, more preferably 90% or more, and particularly 95% or more. Further, depending on the use of the polyimide resin, the sulfhydrylation rate is expected to be close to 100%.

In addition, a known monofunctional acid anhydride or monoamine used in the field may be used in combination as an end capping agent for the purpose of controlling the molecular weight or the like insofar as the effect of the present invention is not impaired. Specific examples of the capping agent are phthalic anhydride belonging to an acid anhydride, maleic anhydride, Nadic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., which are monoamine anilines. Methyl aniline, allylamine, and the like.

III. Polyglycolic acid varnish

The polyamic acid varnish of the present invention is characterized by containing a polyphthalic acid resin and an organic solvent. The organic solvent may be the same as or different from the organic solvent used in the copolymerization reaction between the tetracarboxylic dianhydride and the diamine compound, but it is preferably the same in terms of troubles such as solvent replacement work.

The viscosity of the polyamid varnish is suitable for the intended use, and the viscosity at 25 ° C is preferably in the range of 0.1 to 500 Pa ‧ and the range of 1 to 100 Pa ‧ is better. .

The concentration of the polyamic acid resin in the polyamic acid varnish is preferably adjusted to 5 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 10 to 30% by weight.

Further, when the polyimide film is obtained from the polyamid acid varnish, one part of the organic solvent may be replaced with a low boiling point solvent for the purpose of performing the efficient drying step. Examples of the low boiling point solvent include aromatic hydrocarbons such as toluene, xylene, and solvent petroleum brain, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and dicyclohexane, and ethers such as propylene glycol monomethyl ether. Class, or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone. When such a low boiling point solvent is used, it is preferably used in an amount of from 1 to 30% by weight, more preferably from 5 to 20% by weight, based on the total amount of the organic solvent.

Further, in the polyamic acid varnish of the polyimide precursor of the present invention, other components may be added in the range which does not impair the effects of the present invention. For example, a polyester resin, a polyimide resin (except for the polyimine resin of the present invention), a polymer compound such as a polyamide amine resin, a polyamide resin, a smoothing agent, and a leveling agent. , defoaming agent, flame retardant, antifoaming agent, oxidation inhibitor, etc.

IV. Polyimine varnish

In the polyimine resin of the present invention, (A) bis[4-(4-aminophenoxy)phenyl]fluorene as a diamine component and (B) a diamine compound represented by the above formula (3) The polyimine resin obtained by using at least one of them in combination with the aromatic diamine component and the alicyclic diamine compound is dissolved in a solvent. Therefore, the polyimide resin can be used as a polyimide varnish. The polyimide varnish is characterized by containing a polyimide resin and an organic solvent. The organic solvent may be the same as or different from the organic solvent used in the above-described ruthenium polymerization reaction, but the same is preferable in terms of troubles such as work by solvent replacement.

The preparation method of the polyimide varnish is exemplified by the following methods: (i) a reaction solvent solution of a polyimine resin obtained by hydrazine imidization polymerization directly as a method of a polyimide varnish, (ii) The polyimine resin is separated from the reaction solvent solution of the polyimine resin obtained by the amination polymerization reaction, and then the monomeric polyimide resin is dissolved in a desired organic solvent to obtain a polyimine. The method of varnishing, etc.

The viscosity of the polyimide varnish can be suitably selected according to the intended use, and the viscosity at 25 ° C is preferably in the range of 0.1 to 500 Pa ‧ and the range of 1 to 100 Pa ‧ is better.

The concentration of the polyimide resin in the polyimide varnish is recommended to be adjusted to 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 10 to 30% by weight.

The organic solvent is not particularly limited as long as it is an organic solvent in which the polyimine resin of the present invention can be dissolved. Specifically, the above may be exemplified. The exemplified reaction solvent. These can be used individually or in combination. In this, N-methyl-2-pyrrolidone, 1,3-dimethyltetrahydroimidazolone, N,N-dimethylformamide, N,N-dimethylacetamide, γ - Butyrolactone is receiving a prize.

Further, when the polyimide film is coated with a polyimide film, the low-boiling organic solvent is used for the purpose of preventing coloring of the polyimide film of the polyimide film in the drying step. Specific examples thereof include N,N-dimethylformamide and N,N-dimethylacetamide.

Further, when the polyimide film of the polyimide film is obtained from the polyimide varnish, a part of the organic solvent may be replaced with a solvent having a low boiling point for the purpose of performing the efficient drying step. Examples of the low boiling point solvent include aromatic hydrocarbons such as toluene, xylene, and solvent petroleum brain, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and dicyclohexane, and ethers such as propylene glycol monomethyl ether. Class, or ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone. When such a low boiling point solvent is used, it is preferably used in an amount of from 1 to 30% by weight, more preferably from 5 to 20% by weight, based on the total amount of the organic solvent.

Further, other components may be added to the polyimide varnish tree of the present invention within a range not inhibiting the effects of the present invention. For example, a polyester resin, a polyimide resin (except the polyimine resin of the present invention), a polyamide compound, a polymer compound such as a polyamide resin, a smoothing agent, a leveling agent, Defoaming agent, flame retardant, antifoaming agent, oxidation inhibitor, etc.

The polyimide varnish thus obtained is excellent in storage stability and can be used for various purposes.

V. Polyimine molded body

The polyimine imide molded article of the present invention is obtained by molding a polyamic acid varnish. The method of forming processing is not particularly limited, and a conventional method can be used.

For example, the following method can be exemplified: after the polyamic acid varnish is applied to a substrate (after coating or forming into a film shape, a film shape or a flake shape), the polyamic acid varnish is dried to 200 ° C or higher, preferably 300. Above °C, the hydrazine imidization is heated and the solvent is removed, so that it is formed into a film-like, film-like or flaky polyimine molded body.

Further, the polyimine molded article of the present invention may be obtained by a process for forming a polyimide varnish. The method of forming processing is not particularly limited, and a conventional method can be used.

For example, the following method can be exemplified: after the polyimide varnish is applied to a substrate (coated or formed into a film shape, a film shape or a sheet shape), an organic solvent is removed from the polyimide varnish, and thus formed A film-like, film-like or flaky polyimine molded body film.

Examples of the production of the polyimine molded article include a method of casting a polyamic acid varnish or a polyimide varnish on a PET substrate (polyethylene terephthalate substrate) in a vacuum dryer ( In a decompression degree of 1 to 10 mmHg, it is allowed to stand at room temperature for 30 minutes to 2 hours, and then heated to about 200 ° C in 30 minutes to 2 hours, and the solvent is distilled off at this temperature for 1 to 4 hours. After cooling to room temperature, the polyimide film formed on the PET substrate was taken out by a vacuum dryer and peeled off from the PET substrate. The stripped polyimine film is fixed on a stainless steel metal frame, placed in a vacuum dryer again, and heated from room temperature to 230-330 ° C in 1 to 4 hours. Dry at this temperature for 2 to 5 hours. The solvent was completely distilled off, and after cooling to room temperature, it was taken out from the vacuum dryer to obtain a polyimide film. The thickness of the polyimide film thus obtained is adjusted to the target thickness by adjustment of the thickness of the coating step at the time of casting.

The high transparency of the polyimine resin of the present invention can be evaluated by the total light transmittance. The range of the total light transmittance is preferably 87% or more, more preferably 88% or more, and particularly preferably 89% or more. In the present specification and the patent application, the total light transmittance is a value obtained by the method described in the examples described later. For example, the above-mentioned range of total light transmittance is an effective range in applications where high transparency is particularly required.

The heat resistance of the polyimine resin of the present invention can be evaluated by the glass transition temperature. The glass transition temperature is preferably in the range of 250 ° C or higher, more preferably 260 ° C or higher, and particularly preferably 270 ° C. In the present specification and the patent application, the glass transition temperature is a value obtained by the method described in the examples below. For example, the above-mentioned glass transition temperature range is an effective range in applications where heat resistance is particularly required.

The linear expansion coefficient of the polyimine resin of the present invention is preferably 65 ppm/K or less, more preferably 62 ppm/K or less, and particularly preferably 60 ppm/K or less. In the present specification and the patent application, the coefficient of linear expansion is a value obtained by the method described in the examples described later. For example, the range of the linear expansion coefficient described above is particularly effective in the use of a transparent flexible substrate such as an organic EL.

VI. Plastic substrate / electrical parts ‧ electronic parts

The plastic substrate of the present invention is characterized in that it is composed of the above polyimine molded body. A known manufacturing method can be used for the manufacturing method.

This plastic substrate is particularly suitable for use in, for example, a flexible transparent substrate, because of its high transparency, heat resistance and low coefficient of linear expansion.

Further, the flexible transparent substrate is often used in electrical components or electronic components, and is suitably used as, for example, electronic paper, organic solar cells, organic EL illumination, and flexible liquid crystal displays.

VII. Heat-resistant insulating material / heat-resistant coating / heat-resistant coating material / heat-resistant bonding material

The heat-resistant insulating material, heat-resistant coating material, heat-resistant coating material or heat-resistant adhesive material of the present invention is a polyimide resin using the present invention. The manufacturing method is a conventional manufacturing method. The polyimine resin has high transparency, heat resistance, and low coefficient of linear expansion, and is suitable for use as either.

The embodiments shown below are intended to illustrate the invention in more detail, and the invention is not limited by the examples. Further, in the measurement methods of the respective characteristics in the examples and the comparative examples, the compound abbreviations are as follows.

<compound abbreviated> ‧tetracarboxylic dianhydride

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

DSDA: 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride

‧Aromatic diamine compound

DPE: 4,4'-diaminodiphenyl ether

DAM: 4,4'-diaminodiphenylmethane

BAPP: 2,2-bis[4-(4-aminophenoxy)phenyl]propane

BAPS: bis[4-(4-aminophenoxy)phenyl]indole

BAPB: 4,4'-bis(4-aminophenoxy)biphenyl

TPE-Q: 1,4-bis(4-aminophenoxy)benzene

m-TD: m-tolidine

‧ alicyclic diamine compound

HDAM: 4,4'-methylenebis(cyclohexylamine)

DMHDAM: 3,3'-dimethyl-4,4'-methylenebis(cyclohexylamine)

NBDA: norbornane diamine

‧Reaction solvent

NMP: N-methyl-2-pyrrolidone

DMAc: N,N'-dimethylacetamide

ECH: Ethylcyclohexane

<Polyimide resin, number average molecular weight and weight average molecular weight of poly-proline resin>

Approximately 1 g of a reaction solution (polyimine varnish) or a polyamic acid varnish of the polyimine resin was diluted with about 30 ml of N,N-dimethylformamide to prepare a sample solution for molecular weight measurement. The number average molecular weight (Mn) and the weight average molecular weight (Mw) in terms of polystyrene were determined by gel permeation chromatography (GPC) under the following measurement conditions.

[Measurement conditions]

Device: Tosoh Co., Ltd. EcoSEC HLC-8320GPC

Pipe column: 1 set of SuperH-H made by Tosoh Co., Ltd. and 3 pairs of SuperHM-M

Column temperature: 40 ° C

Dissolution: (5.15 mmol / L - lithium bromide + 5.10 mmol / L - phosphoric acid) / N, N-dimethylformamide

Flow rate: 0.5mL/min

Detector: RI

<Evaluation of solvent solubility>

The solvent solubility was adjusted to 15% by weight after the polymerization reaction of the ruthenium imidization reaction, and the state after leaving it at room temperature for 24 hours was visually observed. When it was considered to be completely free of precipitates or gelled in the reaction solution after standing for 24 hours, it was evaluated as having solubility.

<linear expansion coefficient>

According to JIS K7197 (1991), a polyimide film (40 μm) was heated in a downwind dryer at 300 ° C for 30 minutes for stress relaxation treatment. The 4.0×10.0 mm obtained by the film cutting was measured by the SII NanoTechnology TMA/SS6100, and the range of 100 to 150° C. was measured under the conditions of a nitrogen flow rate of 200 ml/min and a heating rate of 10° C./min. The average value is taken as the coefficient of linear expansion.

<all light transmittance>

According to JIS K7361-1 (1997), a polyimide film (40 μm) was produced using a HAZE-GUARD II manufactured by Toyo Seiki Seisakusho Co., Ltd., and was measured by a single beam method using a D65 light source.

<glass transition temperature>

Dynamic viscoelasticity measuring device RHEOGEL-E4000 (Ure The tan δ of the polyimide film (film) was measured under the following measurement conditions by ban Project Machine. The maximum value of tan δ is taken as the glass transition temperature (°C).

[Measurement conditions]

Measurement mode: stretching mode

Sine wave: 10Hz

Heating rate: 5 ° C / min

Air flow rate: 10L/min

<Mechanical characteristics evaluation>

The elastic modulus of the polyimide film (film), "strength" and "stretching rate" were measured in accordance with JIS K-7161 (1994) using a universal material testing machine 5565 manufactured by Instron.

Manufacturing example

BCODA is made by reference to patent document US3423431. Specifically, 95.0 g (969 mmol) of maleic anhydride and 1,2,3,6-tetrahydrophthalic anhydride were added to five open reaction flasks of 1500 ml internal irradiation type Pyrex (registered trademark) glass. 192.0 g (1262 mmol) and 1200 g of n-butyl acetate were prepared, and the outer wall of the reactor was covered with an aluminum foil and stirred and dissolved at room temperature. Further, nitrogen was bubbled during 15 minutes to remove oxygen in the reaction vessel. Thereafter, the reaction vessel was cooled to 20 ° C while stirring, and light irradiation was performed for 24 hours using a 400 W high-pressure mercury lamp in a light source cooling tube at the center of the triangular flask. After the completion of the reaction, the precipitated crystals were filtered, washed with 60 g of n-butyl acetate, and then dried to obtain 59.9 g (239 mmol, yield: 25%) of BCODA crystals.

Example 1

To a 200 mL Erlenmeyer flask equipped with a stirrer, 136 g of NMP and 11.04 g (52 mol) of m-TD as an aromatic diamine compound were added and stirred for 15 minutes. After BCODA 13.01 g (52 mmol) was added to the obtained solution, the mixture was stirred overnight to obtain a polyamic acid varnish. The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Example 2

The polyamic acid varnish of the present invention was obtained in the same manner as in Example 1 except that the aromatic diamine compound was changed to 10.41 g (52 mmol) of DPE. The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Example 3

The polyamic acid varnish of the present invention was obtained in the same manner as in Example 1 except that the aromatic diamine compound was changed to TPE-Q15.20 g (52 mmol). The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Example 4

The polyamic acid varnish of the present invention was obtained in the same manner as in Example 1 except that the aromatic diamine compound was changed to BAPB 19.16 g (52 mmol). The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Example 5

The polyamic acid varnish of the present invention was obtained in the same manner as in Example 1 except that the aromatic diamine compound was changed to 22.76 g (52 mmol) of BAPS. The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Example 6

The polyamic acid varnish of the present invention was obtained in the same manner as in Example 1 except that the aromatic diamine compound was changed to DAM 10.31 g (52 mmol). The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Comparative example 1

The polyamic acid varnish of the present invention was obtained in the same manner as in Example 2 except that the tetracarboxylic dianhydride was changed from BCODA to 18.63 g (52 mol) of DSDA. The measurement results of the average molecular weight of the polyamic acid resin are shown in Table 1.

Experimental example 1

The polyamic acid varnish obtained in Examples 1 to 6 was coated on a glass substrate with a coating bar to have a dry film thickness of 40 μm, and vacuumed in a vacuum dryer (reduced pressure of 10 mmHg or less), and dried at 300 ° C × 1 After cooling to room temperature, the film was peeled off from the glass substrate to obtain a polyimide film (film). The results of measurement of the linear expansion coefficient, total light transmittance, glass transition temperature, and mechanical properties of the obtained polyimide film (film) are shown in Table 1.

Experimental example 2

The polyamic acid varnish obtained in Comparative Example 1 was coated on a glass substrate with a coating bar to have a dry film thickness of 40 μm, and vacuumed in a vacuum dryer (reduced pressure of 10 mmHg or less) and dried at 300 ° C for 1 hour. After cooling to room temperature, it peeled from the glass substrate, and the polyimine shaped body (film) was obtained. The results of measurement of the linear expansion coefficient, total light transmittance, glass transition temperature, and mechanical properties of the obtained polyimide film (film) are shown in Table 1.

Example 7

A 200 mL four-opening flask containing a thermometer, a stirrer, a nitrogen introduction tube, a liquid separation decanter and a cooling tube was charged with BCODA 13.01 g (52 mmol) and DPE 5.21 g (26 mmol) as an aromatic diamine compound. And BAPS 11.24g (26mmol), DMAc 99g as a reaction solvent, and 11g of ECH as an azeotropic solvent, and the reaction system was replaced with nitrogen, and then the produced water was removed to the system while stirring at 160 ° C under a nitrogen stream. The deuteration imidization polymerization was carried out for 5 hours. After the reaction, DMAc was added to have a resin concentration of 20% by weight, whereby a DMAc solution (polyimine varnish of the present invention) of the polyimine resin of the present invention was obtained. The measurement results of the average molecular weight of the obtained polyimine resin are shown in Table 2.

Example 8

A DMAc solution of the polyimine resin of the present invention was obtained by the same method as in Example 7 except that the aromatic diamine compound was changed to 3.12 g (15.6 mmol) of DPE and 15.74 g (36.4 mmol) of BAPS (the present invention). Polyimide varnish). The measurement results of the average molecular weight of the obtained polyimine resin are shown in Table 2.

Example 9

A DMAc solution of the polyimine resin of the present invention was obtained by the same method as in Example 7 except that the aromatic diamine compound was changed to m-TD4.42 g (20.8 mmol) and BAPS 13.49 g (31.2 mmol). Invention of the polyimide varnish). The measurement results of the average molecular weight of the obtained polyimine resin are shown in Table 2.

Example 10

With thermometer, mixer, nitrogen inlet tube, liquid separation decanter and A 200 mL flask with 4 openings of a cooling tube was charged with BCODA 13.28 g (53.1 mmol), HDAM 5.55 g (26.4 mmol) as an alicyclic diamine compound, and DPE 5.29 g (26.4) as an aromatic diamine compound. (mmol), 123.9 g of DMAc as a reaction solvent, 13.7 g of ECH as an azeotropic solvent, and the reaction system was replaced with nitrogen, and then stirred under a nitrogen stream at 160 ° C, and the produced water was removed from the system while being carried out. 5-hour dehydration hydrazine imidization polymerization. After the reaction, DMAc was added to have a resin concentration of 15% by weight, whereby a DMAc solution (polyimine varnish of the present invention) of the polyimine resin of the present invention was obtained. The measurement results of the average molecular weight of the obtained polyimine resin are shown in Table 2.

Example 11

The polyimine varnish of the present invention was obtained in the same manner as in Example 10 except that the aromatic diamine compound was changed to 5.23 g (26.4 mmol) of DAM. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 12

The polyimine varnish of the present invention was obtained in the same manner as in Example 10 except that the amount of BCODA charged was changed to 12.33 g (49.3 mmol). The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 13

The polycyclic amide of the present invention was obtained by the same method as in Example 12 except that the alicyclic diamine compound was changed to 7.77 g (37.0 mmol) of HDAM and the aromatic diamine compound was changed to 3.17 g (15.8 mmol) of DPE. Amine paint. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 14

The polyimine varnish of the present invention was obtained in the same manner as in Example 12 except that the alicyclic diamine compound was changed to 6.29 g (26.4 mmol) of DMHDAM. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 15

The polyimine varnish of the present invention was obtained in the same manner as in Example 12 except that the alicyclic diamine compound was changed to 2.78 g (13.2 mmol) of HDAM and 2.04 g (13.2 mmol) of NBDA. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 16

The polyimine varnish of the present invention was obtained in the same manner as in Example 12 except that the aromatic diamine compound was changed to 5.23 g (26.4 mmol) of DAM. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 17

The polyimine varnish of the present invention was obtained in the same manner as in Example 12 except that the aromatic diamine compound was changed to 10.84 g (26.4 mmol) of BAPP. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 18

Change the aromatic diamine compound to BAPS 11.42g (26.4m The polyimine varnish of the present invention was obtained in the same manner as in Example 12 except for mol. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 19

The aromatic diamine compound was changed to 9.73 g (26.4 mmol) of BAPB, the reaction solvent was changed to 123.9 g of NMP, and the azeotrope was changed to 13.7 g of xylene, and the same procedure as in Example 12 was carried out. The invention of the polyimide varnish. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 20

The polyimine varnish of the present invention was obtained in the same manner as in Example 19 except that the aromatic diamine compound was changed to 7.72 g (26.4 mmol) of TPE-Q. The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Example 21

Aromatic diamine compound The polyimine varnish of the present invention was obtained in the same manner as in Example 19 except that it was changed to m-TD 5.60 g (26.4 mmol). The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin are shown in Table 2.

Comparative example 2

The polyethylenimine varnish of the present invention was obtained by the same method as that of Example 9 except that BCODA was changed to 11.02 g of DSDA (53.1 mmol). The measurement results of the average molecular weight and solvent solubility of the obtained polyimine resin showed In Table 2.

Experimental example 3

The polyamic acid varnish obtained in Examples 7 to 21 was coated on a glass substrate with a coating bar to have a dry film thickness of 40 μm, and vacuumed in a vacuum dryer (reduced pressure of 10 mmHg or less), and dried at 300 ° C × 1 After cooling to room temperature, the film was peeled off from the glass substrate to obtain a polyimide film (film). The results of measurement of the linear expansion coefficient, total light transmittance, glass transition temperature, and mechanical properties of the obtained polyimide film (film) are shown in Table 2.

Experimental example 4

In the polyimide varnish obtained in Comparative Example 2, a polyimine molded article (film) was obtained in the same manner as in Experimental Example 3. The results of measurement of the linear expansion coefficient, total light transmittance, glass transition temperature, and mechanical properties of the obtained polyimide film (film) are shown in Table 2.

The polyimine resin of the present invention is clearly understood from Table 1, which has a low linear expansion coefficient of 60 ppm/K or less, a high total light transmittance of 87% or more, and an excellent physical property of a high glass transition temperature of 280 ° C or higher. The polyimine resin obtained in Comparative Example 1 had a low linear expansion coefficient, a high glass transition temperature, and a low total light transmittance.

Further, the polyimine resin of the present invention is clearly understood from Table 2, which is a solvent-soluble polyimine resin having a low linear expansion coefficient of 60 ppm/K or less, a high total light transmittance of 87% or more, and Excellent physical properties of high glass transition temperature above 260 °C. The polyimide solubility of the polyimide resin of Comparative Example 2 was good, but the total light transmittance was low.

That is, it can be understood from the above that the polyimine resin of the present invention is a polyimine resin which simultaneously satisfies a low linear expansion coefficient, a high total light transmittance, and a high glass transition temperature.

[Industry use area]

The polyimine resin of the present invention has both high transparency, heat resistance and a low coefficient of linear expansion. Therefore, the polyimine molded article obtained by molding the polyimine varnish of the polyimine resin is suitably used for an optical material such as a display or an illumination. Further, the polyimide resin can be used for a heat-resistant insulating material, a heat-resistant paint, a heat-resistant coated material, and a heat-resistant adhesive.

Claims (21)

A polyimine resin which is a tetracarboxylic dianhydride represented by the formula (1) and an aromatic diamine compound, in terms of a molar ratio, relative to the tetracarboxylic dianhydride 100, the diamine compound In total, the ruthenium imidization polymerization is carried out in the range of 90 to 110: The polyimine resin according to claim 1, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chemical 2] The polyimine resin of claim 1, wherein the aromatic diamine compound is: (A) bis[4-(4-aminophenoxy)phenyl]sulfonic acid, and (B) formula (3) At least one of the compounds represented by the diamine compound: [Chemical 3] A polyimine resin which is a tetracarboxylic dianhydride, an aromatic diamine compound and an alicyclic diamine compound represented by the formula (1) in terms of a molar ratio with respect to the tetracarboxylic dianhydride 100. The total of the diamine compounds is obtained by carrying out a ruthenium iodide polymerization in the range of 90 to 110. The formula (1) [Chemical 4] The polyimine resin according to claim 4, wherein the alicyclic diamine compound is at least one of the compounds represented by the diamine compound of the formula (4): The polyimine resin according to claim 4 or 5, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chem. 6] The polyimine resin according to claim 4 or 5, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (5): [Chem. 7] The polyimine resin according to claim 4 or 5, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (6): [Chemical 8] A poly-proline resin which is a tetracarboxylic dianhydride represented by the formula (1) and an aromatic diamine compound, in terms of a molar ratio, relative to the tetracarboxylic dianhydride 100, the diamine compound The total is obtained by copolymerization in the range of 90 to 110. The polyamic acid resin according to claim 9, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chemical 10] The polyamic acid resin according to claim 10, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (5): [Chem. 11] A polyphthalic acid resin, which is a tetracarboxylic dianhydride, an aromatic diamine compound, and an alicyclic diamine compound represented by the formula (1), in terms of a molar ratio, relative to the tetracarboxylic dianhydride 100. The total of the diamine compounds is obtained by performing ruthenium iodide polymerization in the range of 90 to 110: [Chemical 12] The polyamic acid resin according to claim 12, wherein the alicyclic diamine compound is at least one of the compounds represented by the diamine compound of the formula (4): The polyamic acid resin of claim 12 or 13, wherein the aromatic diamine compound is at least one of the compounds represented by the diamine compound of the formula (2): [Chem. 14] A polyimide varnish comprising the polyimine resin according to any one of claims 3 to 8 and an organic solvent. A polyamic acid varnish comprising the polyphthalic acid resin according to any one of claims 9 to 14 and an organic solvent. A polyimine imide molded article obtained by subjecting the polyimine varnish of claim 15 to a forming process. A polyimine imide molded article obtained by subjecting the polyamic acid varnish of claim 16 to a forming process. The polyimine imide formed article according to claim 17 or 18, wherein the polyimine imide formed body is in the form of a film, a film or a sheet. A plastic substrate comprising the polyimine molded article according to any one of claims 17 to 19. An electrical component or electronic component having a plastic substrate as claimed in claim 20.