阅读说明：本技术 聚酰亚胺化合物及包含该聚酰亚胺化合物的成型物 (Polyimide compound and molded article comprising same ) 是由 五岛敏之 M·S·温 于 2019-02-01 设计创作，主要内容包括：本发明的课题为提供具有高的耐热性及透明性的聚酰亚胺化合物。解决手段为：本发明的聚酰亚胺化合物,其特征在于,为下述通式(1)表示的二胺化合物与下述通式(2)表示的脂环式四羧酸二酐的反应物。[化学式1]<Image he="297" wi="700" file="DDA0002029269470000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>[化学式2]<Image he="384" wi="636" file="DDA0002029269470000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention addresses the problem of providing a polyimide compound having high heat resistance and high transparency. The solving means is as follows: the polyimide compound of the present invention is a reaction product of a diamine compound represented by the following general formula (1) and an alicyclic tetracarboxylic dianhydride represented by the following general formula (2). [ chemical formula 1] [ chemical formula 2])

1. A polyimide compound characterized by being a reaction product of a diamine compound represented by the following general formula (1) and an alicyclic tetracarboxylic dianhydride represented by the following general formula (2),

[ chemical formula 1]

In the formula (1), the reaction mixture is,

R₁～R₈each independently selected from the group consisting of hydrogen, fluorine, substituted or unsubstituted alkyl, and substituted or unsubstituted aromatic group, R₁～R₈At least one of which is a substituted or unsubstituted aromatic group,

[ chemical formula 2]

In the formula (2), the reaction mixture is,

a represents an alicyclic structure.

2. The polyimide compound according to claim 1, wherein A in the general formula (2) has a structure represented by the following formula,

[ chemical formula 3]

3. The polyimide compound according to claim 1 or 2, wherein a content of the diamine compound represented by the general formula (1) in the polyimide compound is 5 mol% or more and 50 mol% or less.

4. The polyimide compound according to any one of claims 1 to 3, wherein the content of the alicyclic tetracarboxylic dianhydride represented by the general formula (2) in the polyimide compound is 10 mol% or more and 60 mol% or less.

5. Diamine compound according to any of claims 1 to 4, wherein R₅～R₈One or both of which are substituted or unsubstituted aromatic groups.

6. Diamine compound according to any of claims 1 to 5, wherein R₅～R₈One or two of them are substituted or unsubstituted aromatic groups, R being other than an aromatic group₁～R₈Selected from the group consisting of hydrogen, fluorine, and substituted or unsubstituted alkyl.

7. Diamine compound according to any of claims 1 to 6, wherein the substituted or unsubstituted aromatic group is selected from the group consisting of phenyl, methylphenyl, phenoxy, benzyl and benzyloxy.

8. Diamine compound according to any of claims 1 to 7, further comprising a fluorene compound as a polymerization component.

9. Diamine compound according to claim 8, wherein the fluorene compound is selected from the group consisting of,

[ chemical formula 4]

[ chemical formula 5]

10. The polyimide compound according to claim 8 or 9, wherein a content of the fluorene compound in the polyimide compound is 5 mol% or more and 60 mol% or less.

11. A molded article comprising the polyimide compound according to any one of claims 1 to 10.

12. A shaped article according to claim 11, which has a total light transmittance of 85% or more.

13. The shaped article according to claim 11 or 12, which has a Coefficient of Thermal Expansion (CTE) of 35ppm/K or less.

14. A shaped product according to any one of claims 11 to 13, which has a 5% weight loss temperature of 420 ℃ or higher.

15. A shaped product according to any one of claims 11 to 14, having a glass transition temperature of 280 ℃ or higher.

Technical Field

The present invention relates to a polyimide compound and a molded article comprising the same.

Background

Generally, a polyimide compound has high heat resistance, and is excellent in mechanical strength, abrasion resistance, dimensional stability, chemical resistance, etc., insulation properties, etc., and thus can be used in various fields.

For example, in recent years, applications to optical applications, display applications, and the like have been advanced, and polyimide compounds applied to such fields are required to have high transparency.

The inventors of the present application proposed a diamine compound having a specific structure in a previous application (Japanese patent application No. 2017-013567).

Disclosure of Invention

Problems to be solved by the invention

The inventors of the present application obtained the following findings this time: the polyimide compound, which is a reactant of the diamine compound and the acid anhydride having a specific structure, proposed in the previous applications is significantly improved in terms of high heat resistance and transparency.

Accordingly, an object to be solved by the present invention is to provide a polyimide compound having high heat resistance and transparency.

Further, an object to be solved by the present invention is to provide a molded article comprising the polyimide compound.

Means for solving the problems

The polyimide compound of the present invention is characterized by being a reaction product of a diamine compound represented by the following general formula (1) and an alicyclic tetracarboxylic dianhydride represented by the following general formula (2).

[ chemical formula 1]

(in the above-mentioned formula,

R₁～R₈each independently selected from the group consisting of hydrogen, fluorine, substituted or unsubstituted alkyl, and substituted or unsubstituted aromatic group, R₁～R₈At least one of which is a substituted or unsubstituted aromatic group. )

[ chemical formula 2]

(in the above-mentioned formula,

a represents an alicyclic structure. )

In one embodiment, a in the general formula (2) has the following structure.

[ chemical formula 3]

In one embodiment, the content of the diamine compound represented by the general formula (1) in the polyimide compound is 5 mol% or more and 50 mol% or less.

In one embodiment, the content of the alicyclic tetracarboxylic dianhydride represented by the general formula (2) in the polyimide compound is 10 mol% or more and 60 mol% or less.

In one embodiment, R₅～R₈One or both of which are substituted or unsubstituted aromatic groups.

In one embodiment, R₅～R₈One or two of which are substituted or unsubstituted aromatic groups, and R other than the aromatic group₁～R₈Selected from the group consisting of hydrogen, fluorine, and substituted or unsubstituted alkyl.

In one embodiment, the substituted or unsubstituted aromatic group is selected from the group consisting of phenyl, methylphenyl, phenoxy, benzyl and benzyloxy.

In one embodiment, the polyimide compound of the present invention further comprises a fluorene compound as a polymerization component.

In one embodiment, the fluorene compound is selected from the following compounds.

[ chemical formula 4]

In one embodiment, the content of the fluorene compound in the polyimide compound is 5 mol% or more and 60 mol% or less.

The molded article of the present invention is characterized by containing the polyimide compound.

In one embodiment, the molded article has a total light transmittance of 85% or more.

In one embodiment, the molded product has a Coefficient of Thermal Expansion (CTE) of 35ppm/K or less.

In one embodiment, the 5% weight loss temperature of the shaped article is 420 ℃ or higher.

In one embodiment, the glass transition temperature of the molded article is 280 ℃ or higher.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a polyimide compound having high heat resistance and transparency can be provided.

Further, the present invention can provide a molded article comprising the polyimide compound.

Drawings

[ FIG. 1] A]FIG. 1 shows a compound represented by the formula (D) obtained by way of example¹H-NMR spectrum.

[ FIG. 2]]FIG. 2 shows a compound represented by the formula (D) obtained in example¹³C-NMR spectrum.

FIG. 3 is a FT-IR spectrum of a compound represented by the formula (D) obtained in example shown in FIG. 3.

Detailed Description

(polyimide Compound)

The polyimide compound of the present invention is characterized by being a reaction product of a diamine compound represented by the following general formula (1) and an alicyclic tetracarboxylic dianhydride represented by the following general formula (2).

[ chemical formula 6]

[ chemical formula 7]

The number average molecular weight of the polyimide compound of the present invention is preferably 2000 to 200000, and more preferably 4000 to 100000.

In the present invention, the number average molecular weight means: values in terms of polystyrene based on a calibration curve prepared using standard polystyrene using a Gel Permeation Chromatography (GPC) apparatus.

By setting the number average molecular weight within the above numerical range, the mechanical properties of a molded article obtained using the polyimide compound can be improved, and moldability can be improved.

The polyimide compound of the present invention can be produced by a conventionally known method using the diamine compound represented by the above general formula (1) and the acid anhydride represented by the above general formula (2). Specifically, the polyimide resin can be obtained by reacting a diamine compound with an acid anhydride to obtain a polyamic acid, and then subjecting the polyamic acid to cyclodehydration reaction to convert the polyamic acid into a polyimide compound.

The mixing ratio of the acid anhydride and the diamine compound is preferably 0.5 to 1.5 mol%, more preferably 0.9 to 1.1 mol%, based on 1 mol% of the total amount of the acid anhydride. This can further improve the heat resistance and transparency of the polyimide compound.

The reaction of the diamine compound with the acid anhydride is preferably carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not react with the diamine compound and the acid anhydride of the present invention and can dissolve the reactant of the diamine compound and the acid anhydride, and examples thereof include N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, N' -dimethylimidazolidinone, γ -butyrolactone, dimethyl sulfoxide, sulfolane, 1, 3-dioxolane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dibutyl ether, dibenzyl ether, and the like, Ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propyl acetate, propylene glycol diacetate, butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, benzyl acetate, diethylene glycol monobutyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl benzoate, ethyl benzoate, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, acetylacetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, 2-heptanone, butanol, isobutanol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol, toluene, xylene, and the like.

From the viewpoint of solubility of the polyimide compound of the present invention, N-methyl-2-pyrrolidone, N' -dimethylimidazolidinone, and γ -butyrolactone are preferable in terms of polyimide.

In the case of chemical imidization, the reaction temperature of the diamine compound and the acid anhydride is preferably 40 ℃ or lower. In addition, in the thermal imidization, preferably 150 to 220 ℃, more preferably 170 to 200 ℃.

In the cyclodehydration reaction, an imidization catalyst may be used, and for example, methylamine, ethylamine, trimethylamine, triethylamine, propylamine, tripropylamine, butylamine, tributylamine, tert-butylamine, hexylamine, triethanolamine, N-dimethylethanolamine, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, aniline, benzylamine, toluidine, trichloroaniline, pyridine, collidine, lutidine, picoline, quinoline, isoquinoline, valerolactone, or the like may be used.

Further, an azeotropic dehydrating agent such as toluene, xylene or ethylcyclohexane, or an acid catalyst such as acetic anhydride, propionic anhydride, butyric anhydride or benzoic anhydride may be used as necessary.

In the reaction of the diamine compound with the acid anhydride, a blocking agent such as benzoic acid, phthalic anhydride, hydrogenated phthalic anhydride, or the like can be used.

Further, a double bond or a triple bond may be introduced to the terminal of the polyimide compound by using maleic anhydride, ethynylphthalic anhydride, methylacetylphthalic anhydride, phenylethynylphthalic anhydride, phenylethynyltrimellitic anhydride, 3-or 4-ethynylaniline, or the like.

The polyimide compound of the present invention can be used as a thermosetting resin by introducing a double bond or a triple bond into the polyimide compound.

(diamine Compound)

The diamine compound used for the synthesis of the polyimide compound of the present invention is characterized by being represented by the following general formula (1).

[ chemical formula 8]

In the above formula, R₁～R₈Each independently selected from the group consisting of hydrogen, fluorine, substituted or unsubstituted alkyl, and substituted or unsubstituted aromatic group, R₁～R₈At least one of which is an aromatic group. Preferably R₁～R₈One or both of which are aromatic groups.

Preferably R₅～R₈One or two of which are substituted or unsubstituted aromatic groups, more preferably at least R₅Or R₇Is an aromatic group.

By having an aromatic group at the above-mentioned position, steric hindrance of the diamine compound can be suppressed, and a polymerization reaction with an acid anhydride or the like can be favorably performed.

In a particularly preferred mode, R₅～R₈One or two of which are substituted or unsubstituted aromatic groups, and R other than the aromatic group₁～R₈Selected from the group consisting of hydrogen, fluorine, and substituted or unsubstituted alkyl.

Specifically, such a compound (R) represented by the following chemical formula (3) may be mentioned₇Is an aromatic group, and R₇R other than₁～R₆And R₈In the form of hydrogen).

[ chemical formula 9]

In the present invention, the alkyl group includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, an alkoxy group and an alkylamino group bonded to the main skeleton via an oxygen atom and a nitrogen atom.

The aromatic group also includes a substituent bonded to the main skeleton via an oxygen atom, a nitrogen atom, and a carbon atom. The aromatic group includes a heteroaromatic group such as a pyrrolyl group.

The alkyl group and the aromatic group are preferably unsubstituted from the viewpoint of ease of synthesis of the diamine compound of the present invention and utilization in the field of electronic component materials, but may have a substituent, and examples thereof include a halogen group such as an alkyl group, a fluoro group, or a chloro group, an amino group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, and a sulfonic acid group. The alkyl group and the aromatic group may have one or more substituents.

The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 3.

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, an n-hexyl group, a cyclohexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a bromomethyl group, a dichloroethyl group, a trichloroethyl group, a bromoethyl group, a dibromoethyl group, a tribromoethyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, a sec-pentyloxy group, an n-hexyloxy group, propylamino, and the like.

Among the above alkyl groups, methyl, ethyl, methoxy, ethoxy and trifluoromethyl are preferable from the viewpoint of steric hindrance and heat resistance.

The number of carbon atoms of the aromatic group is preferably 5 to 20, more preferably 6 to 10.

Examples of the aromatic group having 5 to 20 carbon atoms include phenyl, tolyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, butylphenyl, fluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, benzyl, methoxybenzyl, dimethoxybenzyl, ethoxybenzyl, diethoxybenzyl, aminophenyl, aminobenzyl, nitrophenyl, nitrobenzyl, cyanophenyl, cyanobenzyl, phenethyl, phenylpropyl, phenoxy, benzyloxy, phenylamino, diphenylamino, biphenyl, naphthyl, phenylnaphthyl, diphenylnaphthyl, anthryl, anthrylphenyl, phenylanthryl, tetracenyl, phenanthryl, phenylphenanthryl, pyrenyl, phenylpyryl, fluorenyl, phenylfluorenyl, naphthylethyl, diphenylnaphthyl, anthryl, phenanthryl, phenylphenanthryl, pyrenyl, fluorenyl, phenylfluorenyl, naphthylethyl, etc, And heteroaromatic groups such as a naphthylpropyl group, an anthrylethyl group, a phenanthrylethyl group, or a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, a furyl group, a thienyl group, a triazolyl group, a pyrazolyl group, an isoxazolyl group, an isothiazolyl group, a pyridyl group, a pyrimidinyl group, a benzofuryl group, a benzothienyl group, a quinolyl group, an isoquinolyl group, an indolyl group, a benzothiazolyl group, and a carbazolyl group.

Among the above aromatic groups, phenyl, phenoxy, benzyl and benzyloxy are preferable in terms of starting material ease and synthesis cost.

(method for synthesizing diamine Compound)

The diamine compound can be obtained by: a compound represented by the following general formula (4) is reacted with a compound represented by the following general formula (5), and then the nitro group is reduced.

[ chemical formula 10]

[ chemical formula 11]

In the above formula, R₁’～R₈' each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aromatic group, R₁’～R₈At least one of' is an aromatic group.

Preferably R₅’～R₈At least one of' is a substituted or unsubstituted aromatic group, more preferably at least R₅' or R₇' is an aromatic group.

In a particularly preferred mode, R₅’～R₈One of' is a substituted or unsubstituted aromatic group, and R other than the aromatic group₁’～R₈' is hydrogen.

In the formula, X represents a hydroxyl group or a halogen group selected from a fluoro group, a chloro group, a bromo group and an iodo group. From the viewpoint of reactivity with the compound represented by the general formula (5), X is preferably a halogen group, and particularly preferably a chlorine group or a bromine group.

When X in the general formula (4) is a hydroxyl group, the reaction of the compounds represented by the general formulae (4) and (5) is preferably carried out in the presence of a catalyst or a dehydration condensation agent.

Examples of the catalyst include organic or inorganic basic compounds such as dimethylaminopyridine, tri-n-butylamine, pyridine, lysine, imidazole, sodium carbonate, sodium alkoxide, and potassium hydrogencarbonate, and organic or inorganic acids such as toluenesulfonic acid, methanesulfonic acid, and sulfuric acid.

Examples of the dehydration-condensation agent include carbodiimides such as N, N ' -Dicyclohexylcarbodiimide (DCC), N ' -diisopropylcarbodiimide, and N-cyclohexyl-N ' - (4-diethylamino) cyclohexylcarbodiimide.

In the general formula (4), when X is a halogen group, the reaction of the compounds represented by the general formulae (4) and (5) is preferably carried out in the presence of an acid-binding agent. Specific examples thereof include trialkylamines such as triethylamine, tributylamine and N, N-dimethylcyclohexylamine, aliphatic cyclic tertiary amines such as N-methylmorpholine, aromatic amines such as N, N-dimethylaniline and triphenylamine, and heterocyclic amines such as pyridine, picoline, lutidine and quinoline.

More specifically, the diamine compound represented by the above formula (3) can be obtained by reacting the compounds represented by the following formulae (6) and (7).

[ chemical formula 12]

[ chemical formula 13]

The compound represented by the above general formula (5) can be obtained commercially or by nitrating a synthesized compound represented by the following general formula (8). The nitration of the compound represented by the following general formula (8) can be carried out by a conventionally known nitration method using a mixed acid of concentrated sulfuric acid and concentrated nitric acid, fuming nitric acid, an acid alkali metal salt in concentrated sulfuric acid, acetyl nitrate, a nitronium salt, a nitrogen oxide, and the like.

[ chemical formula 14]

R₅”～R₈"are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl groups, and substituted or unsubstituted aromatic groups. Preferably R₅”～R₈At least one of "is an aromatic group, and more preferably one or two are aromatic groups.

The content of the diamine compound represented by the general formula (1) in the polyimide compound is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 40 mol% or less. This can further improve the heat resistance and transparency of the polyimide compound.

(alicyclic tetracarboxylic acid dianhydride)

The alicyclic tetracarboxylic dianhydride used for synthesizing the polyimide compound of the present invention is characterized by being represented by the following general formula (2).

[ chemical formula 15]

In the above formula, A represents an alicyclic structure. Examples of the alicyclic structure include the following structures.

[ chemical formula 16]

Therefore, specific examples of the alicyclic tetracarboxylic dianhydride include the following compounds. The polyimide compound may contain two or more kinds of alicyclic tetracarboxylic dianhydrides. The following compounds may have a substituent, and examples thereof include a halogen group such as an alkyl group, a fluoro group, or a chloro group, an amino group, a nitro group, a hydroxyl group, a cyano group, a carboxyl group, and a sulfonic acid group. Among these, an alkyl group is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

[ chemical formula 17]

[ chemical formula 18]

Among the tetracarboxylic dianhydrides, the following compounds are preferable from the viewpoint of the heat resistance and transparency of the polyimide compound, and from the viewpoint of the transparency of the polyimide compound.

[ chemical formula 19]

The content of the alicyclic tetracarboxylic dianhydride represented by the general formula (2) in the polyimide compound is preferably 10 mol% or more and 60 mol% or less, and more preferably 20 mol% or more and 50 mol% or less. This can further improve the heat resistance and transparency of the polyimide compound.

(fluorene compound)

In one embodiment, the polyimide compound may include a fluorene compound as a polymerization component. This can reduce the retardation of the polyimide compound while maintaining the heat resistance thereof.

In the present invention, the fluorene compound may be a diamine compound having a fluorene structure or may be an acid anhydride having a fluorene structure.

Examples of the diamine compound having a fluorene structure include the following compounds.

[ chemical formula 20]

Examples of the acid anhydride having a fluorene structure include the following compounds.

[ chemical formula 21]

The content of the fluorene compound in the polyimide compound is preferably 5 mol% or more and 60 mol% or less, and more preferably 15 mol% or more and 50 mol% or less. This can further reduce the retardation while maintaining the heat resistance of the polyimide compound.

(other diamine Compound)

The polyimide compound of the present invention may contain a diamine compound other than the diamine compound represented by the above general formula (1) as a polymerization component (hereinafter, referred to as another diamine compound). Examples of the other diamine compound include 2, 2 ' -bis (trifluoromethyl) benzidine, m-phenylenediamine, p-phenylenediamine, 2, 4-diaminotoluene, 2, 4(6) -diamino-3, 5-diethyltoluene, 5(6) -amino-1, 3, 3-trimethyl-1- (4-aminophenyl) indane, 4 ' -diamino-2, 2 ' -dimethyl-1, 1 ' -biphenyl, 4 ' -diamino-3, 3 ' -dimethyl-1, 1 ' -biphenyl, 3, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenyl ether, 3, 3 ' -diaminodiphenyl sulfone, 4 ' -diaminodiphenyl sulfone, and the like, 4, 4 '-diaminodiphenylsulfide, 4-aminophenyl 4-aminobenzoate, 4' - (9-fluorenylidene) diphenylamine, 9 '-bis (3-methyl-4-aminophenyl) fluorene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 2-bis (4-aminophenyl) propane, 2-bis (3-methyl-4-aminophenyl) propane, 4' - (hexafluoroisopropylidene) dianiline, 2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, α -bis [4- (4-aminophenoxy) phenyl ] -1, 3-diisopropylbenzene, α -bis [4- (4-aminophenoxy) phenyl ] -1, 4-diisopropylbenzene, 3, 7-diamino-dimethyldibenzothiophene 5, 5-dioxide, bis (3-carboxy-4-aminophenyl) methane, 3 '-diamino-4, 4' -dihydroxy-1, 1 '-biphenyl, 4' -diamino-3, 3 '-dihydroxy-1, 1' -biphenyl, 2-bis (3-amino-4-hydroxyphenyl) propane, toluene, xylene, 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 1, 3-bis (3-hydroxy-4-aminophenoxy) benzene, 2-bis (3-hydroxy-4-aminophenyl) benzene, 3 '-diamino-4, 4' -dihydroxydiphenylsulfone and the like.

Among the above, 2 ' -bis (trifluoromethyl) benzidine, 5(6) -amino-1, 3, 3-trimethyl-1- (4-aminophenyl) -indane, 3, 3 ' -diaminodiphenyl sulfone, and 4, 4 ' -diaminodiphenyl sulfone are preferable.

The polyimide compound can have a reduced thermal expansion coefficient when a diamine compound having a benzidine skeleton is used as a polymerization component, and can have improved transparency when a diamine compound having an indane skeleton or a sulfone skeleton is used.

The content of the other diamine compound in the polyimide compound of the present invention is preferably 5 mol% or more and 70 mol% or less, and more preferably 15 mol% or more and 60 mol% or less. This can provide a transparent polyimide having excellent heat resistance.

(other acid anhydrides)

The polyimide compound of the present invention may contain, as a polymerization component (hereinafter, referred to as another acid anhydride), an acid anhydride other than the acid anhydride represented by the above general formula (2). Examples of the other acid anhydride include oxydiphthalic acid, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3, 6-difluoropyromellitic dianhydride, 3, 6-bis (trifluoromethyl) pyromellitic dianhydride, 1, 2, 3, 4-pyromellitic dianhydride, 2 ', 3, 3' -benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4' -biphenyl sulfone tetracarboxylic dianhydride, 4, 4 '- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, 1, 2, 4, 5-cyclohexane tetracarboxylic dianhydride, 2, 3, 3 ', 4' -biphenyl tetracarboxylic dianhydride, 3, 3 ", 4, 4 '-terphenyltetracarboxylic dianhydride, 3, 3', 4, 4 '-tetrabiphenyltetracarboxylic dianhydride, 2', 3, 3 '-biphenyltetracarboxylic dianhydride, methylene-4, 4' -bisphthalic anhydride, 1-ethylene-4, 4 '-bisphthalic anhydride, 2-propylene-4, 4' -bisphthalic anhydride, 1, 2-ethylene-4, 4 '-bisphthalic anhydride, 1, 3-propylene-4, 4' -bisphthalic anhydride, 1, 4-butylene-4, 4 '-bisphthalic anhydride, 1, 5-pentylene-4, 4' -bisphthalic anhydride, 1, 3-bis [ 2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, 1, 4-bis [ 2- (3, 4-dicarboxyphenyl) -2-propyl ] benzene dianhydride, bis [ 3- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, bis [4- (3, 4-dicarboxyphenoxy) phenyl ] methane dianhydride, 2, 2-bis [ 3- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, 2, 2-bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane dianhydride, difluoromethylene-4, 4 ' -biphthalic anhydride, 1, 2, 2-tetrafluoro-1, 2-ethylene-4, 4 ' -biphthalic anhydride, 3 ', 4, 4 '-diphenylsulfone tetracarboxylic dianhydride, 4' -oxydiphthalic anhydride, bis (3, 4-dicarboxyphenyl) ether dianhydride, 4 '-thiobisphthalic anhydride, sulfonyl-4, 4' -bisphthalic anhydride, 1, 3-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenyl) benzene dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (3, 4-dicarboxyphenoxy) benzene dianhydride, bis (3, 4-dicarboxyphenoxy) dimethylsilane dianhydride, 1, 3-bis (3, 4-dicarboxyphenoxy) -1, 1, 3, 3-tetramethyldisiloxane dianhydride, 2, 3, 6, 7-naphthalene tetracarboxylic dianhydride, 1, 2, 5, 6-naphthalene tetracarboxylic dianhydride, 3, 4, 9, 10-perylene tetracarboxylic dianhydride, 2, 3, 6, 7-anthracene tetracarboxylic dianhydride, 1, 2, 7, 8-phenanthrene tetracarboxylic dianhydride, 1, 2, 3, 4-butane tetracarboxylic dianhydride, 3 ', 4, 4' -dicyclohexyl tetracarboxylic dianhydride, carbonyl-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, methylene-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 1, 2-ethylene-4, 4 '-bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 4, 4' -oxybis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 4, 4 '-thiobis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, sulfonyl-4, 4' -bis (cyclohexane-1, 2-dicarboxylic acid) dianhydride, 3 ', 5, 5' -tetrakis (trifluoromethyl) oxy-4, 4 '-bisphthalic anhydride, 3', 6, 6 '-tetrakis (trifluoromethyl) oxy-4, 4' -bisphthalic anhydride, 5, 5 ', 6, 6' -tetrakis (trifluoromethyl) oxy-4, 4 '-bisphthalic anhydride, 3', 5, 5 ', 6, 6' -hexa (trifluoromethyl) oxy-4, 4 '-bisphthalic anhydride, 3' -difluorosulfonyl-4, 4 '-bisphthalic anhydride, 5, 5' -difluorosulfonyl-4, 4 ' -Biphthalic anhydride, 6, 6 ' -difluorosulfonyl-4, 4 ' -Biphthalic anhydride, 3 ', 5, 5 ', 6, 6 ' -hexafluorosulfonyl-4, 4 ' -Biphthalic anhydride, 3 ' -bis (trifluoromethyl) sulfonyl-4, 4 ' -Biphthalic anhydride, 5, 5 ' -bis (trifluoromethyl) sulfonyl-4, 4 ' -Biphthalic anhydride, 6, 6 ' -bis (trifluoromethyl) sulfonyl-4, 4 ' -Biphthalic anhydride, 3 ', 5, 5 ' -tetrakis (trifluoromethyl) sulfonyl-4, 4 ' -Biphthalic anhydride, 3 ', 6, 6 ' -tetrakis (trifluoromethyl) sulfonyl-4, 4 ' -Biphthalic anhydride, 5, 5 ', 6, 6 ' -tetrakis (trifluoromethyl) sulfonyl-4, 4 ' -biphthalic anhydride, 3 ', 5, 5 ', 6, 6 ' -hexa (trifluoromethyl) sulfonyl-4, 4 ' -biphthalic anhydride, 3 ' -difluoro-2, 2-perfluoropropylene-4, 4 ' -biphthalic anhydride, 5, 5 ' -difluoro-2, 2-perfluoropropylene-4, 4 ' -biphthalic anhydride, 6, 6 ' -difluoro-2, 2-perfluoropropylene-4, 4 ' -biphthalic anhydride, 3 ', 5, 5 ', 6, 6 ' -hexafluoro-2, 2-perfluoropropylene-4, 4 ' -biphthalic anhydride, bis-phthalic anhydride, 3, 3 '-bis (trifluoromethyl) -2, 2-perfluoropropylidene-4, 4' -biphthalic anhydride, ethylene glycol bistrimellitic dianhydride, and the like.

(in the case where the molar% of the whole is also% of the total, it may be more preferable to make it half) the content of the other acid anhydride in the polyimide compound of the present invention is preferably 30 mol% or less, more preferably 25 mol% or less. This can provide a transparent polyimide having excellent film properties and heat resistance.

(use)

The polyimide compound of the present invention can be used for, for example, the following applications: a case used for a personal computer, a mobile phone, or the like, an electronic material component such as a flexible printed circuit board or a printed wiring board, a component for an image display device such as an organic EL display device, a component for a touch panel, a surface protective layer, a component for a solar cell panel such as a substrate, or the like.

(Molding)

The molded article of the present invention is characterized by containing the polyimide compound.

The shape of the molded article of the present invention is not particularly limited, and may be appropriately modified depending on the use. For example, the film-like material may be in the form of a film or a sheet.

The content of the polyimide compound in the molded article of the present invention is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and still more preferably 60% by mass or more and 100% by mass or less.

The molded article of the present invention may contain other compounds within a range not impairing the properties thereof, and examples thereof include polyolefin-based resins, polyester-based resins, cellulose-based resins, vinyl-based resins, polycarbonate-based resins, polyamide-based resins, styrene-based resins, ionomer resins, and the like.

The molded article of the present invention may contain various additives within a range not impairing the properties thereof. Examples of the additives include plasticizers, ultraviolet stabilizers, coloring inhibitors, matting agents, deodorants, flame retardants, weather resistant agents, antistatic agents, yarn friction reducing agents (Japanese "system friction reducing agents"), slip agents, mold release agents, antioxidants, ion exchangers, dispersants, ultraviolet absorbers, and colorants such as pigments and dyes.

The molded article of the present invention preferably has a total light transmittance of 85% or more, more preferably 90% or more.

In the present invention, the total light transmittance of the molded article can be measured according to JIS K7136 and 7375.

The Coefficient of Thermal Expansion (CTE) of the shaped product of the present invention is preferably 35ppm/K or less, more preferably 30ppm/K or less, and still more preferably 25ppm/K or less.

In the present invention, the Coefficient of Thermal Expansion (CTE) of the molded product is: the molded article was heated from room temperature to 450 ℃ at a temperature of 10 ℃ per minute while applying a load of 5g to the molded article, and an average Coefficient of Thermal Expansion (CTE) of 100 ℃ to 250 ℃ was measured using TMA-60 (trade name) manufactured by Shimadzu corporation.

The 5% weight reduction temperature of the shaped product of the present invention is preferably 420 ℃ or higher, more preferably 450 ℃ or higher.

In the present invention, the 5% weight loss temperature of the molded article can be measured in nitrogen at a temperature rise rate of 5 ℃ per minute using a thermomechanical analyzer (for example, TGA-50, manufactured by Shimadzu corporation) in accordance with JIS K7120.

The glass transition temperature (Tg) of the molded article of the present invention is preferably 280 ℃ or higher, more preferably 300 ℃ or higher, and still more preferably 340 ℃ or higher.

In the present invention, the glass transition temperature (Tg) of the molded article can be measured according to JIS K7121 at a temperature rising rate of 10 ℃ per minute under a nitrogen stream using a thermomechanical analyzer (product name: DSC-60Plus, manufactured by Shimadzu corporation).

(method for producing molded article)

In one embodiment, the shaped article of the present invention can be produced by: the polyimide compound is dissolved in the organic solvent such as N-methyl-2-pyrrolidone (NMP), applied to a substrate such as a copper foil, and dried. Thus, a film-shaped molded product can be obtained.

The substrate may be removed by peeling it from the molded article or by etching, depending on the application.

The molded article using the polyimide compound of the present invention can be produced by only the step of coating a base material with a polyisoimide compound or a polyimide compound and drying the coating, and the step of heating and drying at a high temperature associated with the imidization reaction, which is carried out in the conventional method, can be omitted. Further, since the heat drying step can be omitted, the molded article of the present invention can be produced on various substrates without considering the heat resistance of the substrate.

The molded article of the present invention may be produced by a conventionally known method such as press molding, transfer molding, or injection molding.