TW201425473A - Composition for heat-resistant substrate - Google Patents

Abstract

To provide a composition that imparts a cured film appropriate for a display substrate material having high strength, high heat resistance, the appropriate linear expansion coefficient, and high transparency. A composition for a heat-resistant substrate comprising an organic solvent and at least one selected from the group consisting of a polyimide precursor having structural units represented by formula (1), structural units represented by formula (2), and structural units represented by formula (3), and imidized polymers thereof. (In formulas (1) through (3), X1 is a tetravalent group represented by formula (4), Y1, Y2, and Y3 are divalent groups represented by formulas (5), (6), and (7), respectively, and R1 through R24 are hydrogen atoms, etc.)

Description

Heat resistant substrate composition

The present invention relates to a composition for a heat resistant substrate, and more particularly relates to a heat resistant substrate which is provided with a cured film of a substrate material suitable for an electronic device, particularly a display, which has high strength, high heat resistance, moderate linear expansion coefficient, and high transparency. Use the composition.

In recent years, in the field of display devices such as organic electroluminescent elements (hereinafter also referred to as organic EL) displays and liquid crystal displays, demands for ultra-thinness, light weight, and flexibility have been increasing, and resin materials as substrate materials have been increasing. Received attention.

However, in high-definition displays, active matrix-driven panels have been used. In the manufacturing process, in addition to the matrix-shaped pixel electrodes, the active matrix layer including the thin film active elements is formed not only at a high temperature of 200 ° C or higher, but also very necessary. Correct position adjustment. Therefore, when a resin material is used as a substrate material for such a display in place of glass, it is difficult to satisfy heat resistance and dimensional stability.

For this, as heat resistance or dimensional stability can be avoided There are several proposals for resin materials. For example, Patent Document 1 discloses a polyimide film for a display substrate obtained by using a tetracarboxylic dianhydride having an alicyclic structure and various diamines, and disclosed in Patent Document 2 A polyimide film for a display substrate obtained by using the obtained polyimine obtained from an aromatic diamine containing an alicyclic tetracarboxylic dianhydride having a cyclohexane skeleton and a mercapto group.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-231327

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-297360

However, although the substrate material of the display is required to have high transparency, the tetracarboxylic dianhydride used in Patent Document 1 contains an aromatic group and uses a tetracarboxylic acid formed from an alicyclic hydrocarbon group not containing an aromatic group. Compared with the dianhydride phase, there is a problem that the transparency of the film is lowered due to the intramolecular conjugate or charge transfer interaction of the polyimine chain.

Further, the acid dianhydride used in Patent Document 2 lacks versatility because it is a condensed tetracarboxylic dianhydride having a special structure such as a cis-structured cyclohexane skeleton, and the polyimine is used when the technique described in the literature is used. Manufacturing costs are high and there is room for improvement at this point.

Therefore, it can be produced using a highly versatile acid dianhydride, although A material which is required for the display substrate, but is a 1,2,3,4-cyclobutane tetracarboxylic dianhydride which is used as an alicyclic tetracarboxylic dianhydride which is synthesized by polyimine. (hereinafter also referred to as CBDA), the ruthenium imidization reaction of the polyimine precursor derived therefrom is difficult to cause due to stereoscopic structural reasons, and a higher temperature is required in order to complete the reaction because the system becomes a poly The reason for the coloration of the quinone imine film is that it is not advantageous to use CBDA as a raw material for the polyimide substrate for the display substrate, and it can be produced by using CBDA. The material suitable for the display substrate has not been proposed yet, but the development of such a material has not been proposed. Has become a topic.

The present invention has been made in view of the above, and a highly versatile tetracarboxylic dianhydride is used to provide a composition for imparting high strength, high heat resistance, moderate linear expansion coefficient, and high transparency. a film obtained from the composition, a substrate material formed by the film, a polyimide precursor contained in the composition, and a ruthenium imidized polymer of the polyimide precursor.

In order to achieve the above object, the inventors of the present invention have found that 1,2,3,4-cyclobutanetetracarboxylic dianhydride, a biphenyldiamine having a perfluoroalkyl group, and an imidazole skeleton are contained. a diamine of a benzene skeleton selected from at least one of a polyimine precursor derived from a phenylenediamine and a quinone imidized polymer thereof, and a composition of an organic solvent, having sufficient film strength At the same time as moderate softness, it has the heat resistance necessary for the formation process of the thin film transistor (TFT), the appropriate coefficient of linear expansion and high The transparency is achieved to complete the present invention.

That is, the present invention provides a composition for a heat resistant substrate comprising a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a formula (3). a polyimine imine precursor of the structural unit and at least one of the group formed by the quinone imidized polymer and an organic solvent, In the formula (1) to the formula (3), X ¹ represents a tetravalent group represented by the formula (4). (In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms; and Y ¹ represents a formula (5). The basis of the price of 2 (In the formula (5), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. ); Y ² represents a divalent base represented by the formula (6), [In the formula (6), R ¹³ to R ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms; (However, at least two of R ¹³ to R ²⁰ represent a perfluoroalkyl group having 1 to 6 carbon atoms); Y ³ represents a divalent group represented by the formula (7). (In the formula (7), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. The composition for a heat resistant substrate according to the above, wherein the Y ¹ system represents a divalent group represented by the formula (8). (In the formula (8), R ⁵ to R ¹² represent the same meaning as described above), and the composition for heat resistant substrate according to 1. or 2. wherein the R ⁵ represents a hydrogen atom, and the above R ⁶ ~ R ¹² each independently represent a hydrogen atom or a perfluoroalkyl group having a carbon number of 1 to 6, 4. 3 1. to. any one of the heat resistant substrate with the composition, wherein the lines represented by the formula Y ² (9 ) the base of the two prices shown, In the formula (9), R ¹³ to R ^{20 are the} same as those in the above-mentioned, and the composition for heat-resistant substrate according to any one of the above-mentioned items, wherein the R ¹³ to R ²⁰ are independent of each other. A composition for a heat resistant substrate according to any one of the above aspects, wherein the Y ³ system is represented by the formula (10). 2 price base, (In the formula (10), R ²¹ to R ^{24 are the} same as the above-mentioned ones, and the composition for heat-resistant substrates according to any one of the above-mentioned items, wherein R ²¹ to R ²⁴ are independent of each other. A composition for a heat-resistant substrate of any one of the above-mentioned R ¹ to R ⁴ , wherein the above-mentioned R ¹ to R ⁴ represents a hydrogen atom, Or a trifluoromethyl group, a film of the substrate for heat-resistant substrate according to any one of the above-mentioned items, which is obtained by heating and obtaining a substrate material. The substrate material described in 9. The substrate material described in 10., which is a substrate for display substrate, 12. a polyimine precursor, which comprises a structural unit represented by formula (1). (2) The structural unit shown and the structural unit shown in the formula (3), In the formula (1) to the formula (3), X ¹ represents a tetravalent group represented by the formula (4). (In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms; and Y ¹ represents a formula (5). The basis of the price of 2 (In the formula (5), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. ); Y ² represents a divalent base represented by the formula (6), [In the formula (6), R ¹³ to R ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms; (However, at least two of R ¹³ to R ²⁰ represent a perfluoroalkyl group having 1 to 6 carbon atoms); Y ³ represents a divalent group represented by the formula (7). (In the formula (7), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. )}, 13. A ruthenium imidized polymer of a polyimide precursor such as 12.

The composition for a heat resistant substrate of the present invention is formed by a wet process such as a spin coating method and heated to provide a film having high strength, high heat resistance, appropriate linear expansion coefficient, and high transparency. Especially in the field of displays in recent years, the film that meets the requirements can therefore help Advances in the field of devices such as organic EL displays and liquid crystal displays.

Further, according to the present invention, it is possible to provide a substrate material suitable for use in a display by the film of the present invention.

Further, according to the present invention, it is possible to provide a polyimine which imparts high strength, high heat resistance, appropriate linear expansion coefficient and high transparency to a film obtained by hardening a composition by being contained in the above composition. Precursor and ruthenium iodide polymer.

The invention is described in detail below.

The composition for a heat resistant substrate of the present invention comprises a polyimine precursor selected from the group consisting of a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3). And at least one of the group formed by the ruthenium imidized polymer;

In the present invention, the ruthenium iodide polymer is a quinone imine group which is reacted with a carboxyl group in the polyimine precursor, and includes at least one selected from the group consisting of the formula (11) to the formula (19). 1 species.

In the formulae (1) to (19), X ¹ represents a tetravalent group represented by the formula (4).

In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms.

Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, and a t-butyl group. Base, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, N-hexyl and the like.

The perfluoroalkyl group having 1 to 6 carbon atoms is a group in which all of the hydrogen atoms in the alkyl group having 1 to 6 carbon atoms are substituted by a fluorine atom.

Specific examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoro-n-propyl group, a heptafluoro-i-propyl group, a nonafluoro-n-butyl group, a nonafluoro-i-butyl group, and a ninth group. Fluorine-s-butyl, nonafluoro-t-butyl and the like.

Among these, in consideration of the balance between the transparency of the obtained cured film and the heat resistance, R ¹ to R ^{4 are} preferably a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably all of them are hydrogen atoms.

In the formula (1) and the formulae (11) to (13), Y ¹ represents a divalent group represented by the formula (5).

In the formula (5), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms.

Examples of the aromatic group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 2-fluorenyl group, a 9-fluorenyl group, a 1-phenanthryl group, and a 2-phenanthrene group. Base, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and the like.

Examples of the alkyl group having 1 to 6 carbon atoms and the perfluoroalkyl group having 1 to 6 carbon atoms are the same as those described above.

As an example of the divalent group represented by the formula (5), the formula (8) can be cited. The base of the two prices shown.

In the formula (8), R ⁵ to R ^{12 have} the same meanings as described above.

In particular, in consideration of the balance between the transparency and the heat resistance of the obtained cured film, in the formulae (5) and (8), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ to R ¹² represent a hydrogen atom or a carbon atom. A perfluoroalkyl group of 1 to 6 is preferred, and R ⁵ to R ¹² are more preferably a hydrogen atom.

In the formula (2) and the formulae (14) to (16), Y ² represents a divalent group represented by the formula (6).

In the formula (6), R ¹³ to R ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. However, at least two of R ¹³ to R ²⁰ represent a perfluoroalkyl group.

Examples of the alkyl group having 1 to 6 carbon atoms, the perfluoroalkyl group having 1 to 6 carbon atoms, and the aromatic group having 6 to 14 carbon atoms are the same as those described above.

Examples of the divalent group represented by the formula (6) include a divalent group represented by the formula (9).

In the formula (9), R ¹³ to R ^{20 have} the same meanings as described above.

In particular, in consideration of the balance of the heat resistance of the obtained cured film, in the formulae (6) and (9), 2 to 4 of R ¹³ to R ²⁰ represent a perfluoroalkyl group having 1 to 6 carbon atoms, and It is preferable that a hydrogen atom is represented, and 2 to 4 of R ¹³ to R ²⁰ represent a perfluoroalkyl group having 1 to 4 carbon atoms, and a hydrogen atom is more preferable.

In the formula (3) and the formula (17) to the formula (19), Y ³ represents a divalent group represented by the formula (7).

In the formula (7), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms.

As an alkyl group having 1 to 6 carbon atoms and a perfluoroalkane having 1 to 6 carbon atoms Examples of the aromatic group having 6 to 14 carbon atoms and the same are the same as those described above.

Examples of the divalent group represented by the formula (7) include a divalent group represented by the formula (10).

In the formula (10), R ²¹ to R ^{24 have} the same meanings as described above.

In particular, in consideration of the balance of the heat resistance of the obtained cured film, in the formulae (7) and (10), R ²¹ to R ^{24 are} preferably a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms. It is more preferably a hydrogen atom or a trifluoromethyl group, and more preferably a hydrogen atom.

a combination of X ¹ and Y ¹ to Y ³ , wherein R ¹ to R ⁴ represent a tetravalent group represented by the formula (4) of a hydrogen atom, a methyl group or a trifluoromethyl group; and a hydrogen atom or a methyl group represented by R ⁵ , R ⁶ to R ¹² represent a divalent group represented by the formula (5) of a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms; and 2 to 4 of R ¹³ to R ²⁰ represent a carbon number of 1 a perfluoroalkyl group of ~6, and a divalent group represented by the formula (6) representing a hydrogen atom; and a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms represented by R ²¹ to R ²⁴ The divalent group represented by the formula (7) is preferred, and R ¹ to R ⁴ represent a tetravalent group represented by the formula (4) of a hydrogen atom, a methyl group or a trifluoromethyl group; and a hydrogen atom represented by R ⁵ Or a methyl group, R ⁶ to R ¹² represent a divalent group represented by the formula (8) of a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms; and 2 to 4 of R ¹³ to R ²⁰ represent carbon a perfluoroalkyl group having 1 to 6 atomic atoms, and a divalent group represented by the formula (9) representing a hydrogen atom; and a hydrogen atom or a perfluoro group having 1 to 6 carbon atoms represented by R ²¹ to R ²⁴ The divalent group represented by the formula (10) of the alkyl group is more preferable, and all of R ¹ to R ⁴ represent a tetravalent group represented by the formula (4) of a hydrogen atom; and all of R ⁵ to R ¹² represent a hydrogen atom. The two-valent one shown in the formula (8) ; R ¹³ ~ R ²⁰ in the 2 to 4 carbon atoms, represents a perfluoroalkyl group of 1 to 4, except that the expression (9) of the divalent group represented by hydrogen atoms; and R ²¹ ~ R to Further, all of ²⁴ represents a divalent group represented by the formula (10) of a hydrogen atom.

Hereinafter, an example of a divalent base represented by the formula (9) is shown, but these are not limited thereto.

The weight average molecular weight of the polyimine precursor and the ruthenium iodide polymer is preferably 3,000 to 150,000 in terms of polystyrene. Weight flat When the average molecular weight is less than 3,000, the film obtained may become brittle, and when it exceeds 150,000, the viscosity of the composition (varnish) may become too high, and as a result, handling may become difficult.

Number of Number of structural units of the number of structural units of polyimide precursors of formula (1) of the structural unit of n ^1, as shown in the formula ⁽²⁾ n 2 and shown in the formula ⁽³⁾ n 3 n to satisfy ² / (n ¹ + n ³ ) = 70 / 30 ~ 99 / 1 is better, preferably 75 / 25 ~ 95 / 5.

Further, it is preferable that n ¹ and n ³ satisfy n ¹ /n ³ =10/90 to 90/10, and it is preferable to satisfy n ¹ /n ³ =40/60 to 60/40.

The solvent to be used in the preparation of the composition of the present invention is not particularly limited as long as it is a solvent which can dissolve the polyimine precursor or the quinone imidized polymer.

As such a solvent, for example, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidine can be cited. Ketone, decyl hexamethyl phosphate, dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis(2- Aprotic solvent such as methoxyethyl)ether, tetrahydrofuran, 1,4-dioxane, methylpyridine, pyridine, acetone, chloroform, toluene, xylene, etc., and phenol, o-cresol, m-cresol A protic solvent such as p-cresol, o-chlorophenol, m-chlorophenol or p-chlorophenol may be used in an amount of 5 to 100% by mass based on the total amount of the solvent to be used. These solvents may be used alone or in combination of two or more.

Further, cyclohexanol, ethylene glycol, 1,3-octanediol, and diethylene glycol may be used for the purpose of improving the wettability of the substrate, adjusting the surface tension of the solvent, adjusting the polarity, and adjusting the boiling point. Dipropylene glycol, triethylene glycol Alcohol, tripropylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, propylene glycol, hexanediol, etc., which do not dissolve polyimine or ruthenium iodide polymers well. The solvent is added to the composition within a range in which the polyimine precursor or the quinone imidized polymer does not precipitate. These solvents may be used alone or in combination of two or more.

The composition of the present invention can be produced by dissolving the above polyimine precursor and/or polyimine polymer in the above solvent. Further, the reaction liquid obtained by the reaction of the polyimine precursor described later may be used as a composition of the present invention as it is, directly or concentrated or diluted.

The concentration of the polyimine precursor and the ruthenium iodide polymer of the composition of the present invention is usually 5 to 40% by mass based on the total mass (total mass) of the solvent to be used, but the storage stability of the composition is considered. In the case of sex, it is preferably from 8 to 30% by mass, more preferably from 10 to 20% by mass.

The composition of the present invention may contain a crosslinking agent (hereinafter also referred to as a crosslinkable compound) within a range that does not greatly impair the heat resistance, transparency, linear expansion coefficient, and flexibility of the obtained film.

The crosslinkable compound is a step of converting a coating film obtained by using the composition of the present invention into a cured film, and having an organic substance which is compatible with at least one of a polyimide intermediate and a ruthenium imidized polymer. The compound which reacts with a group is not particularly limited, and examples thereof include a compound containing two or more epoxy groups or a hydrogen atom of an amine group, which is a methylol group, an alkoxymethyl group or both. A melamine derivative, a benzoguanamine derivative or a glycol urea or the like. The melamine derivative and the benzoguanamine derivative may be a dimer or a trimer, and may be any one selected from the group consisting of a monomer, a 2-mer and a 3-mer. mixture. These crosslinking agents may be used alone or in combination of two or more.

Hereinafter, specific examples of the crosslinkable compound are listed, but are not limited thereto.

Examples of the compound containing two or more epoxy groups include EPOLEAD GT-401, EPOLEAD GT-403, EPOLEAD GT-301, EPOLEAD GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (manufactured by Daicel), and the like. Epoxy compounds of cyclohexane structure; Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above Japanese epoxy resin) (now Mitsubishi Chemical Co., Ltd.) , bisphenol A type epoxy compound such as jER (registered trademark) series); Epikote 807 (Japanese epoxy resin (shares) (now Mitsubishi Chemical Co., Ltd., now jER (registered trademark) series)) And other bisphenol F-type epoxy compounds; Epikote 152, Epikote 154 (above is Japanese epoxy resin (shares) (now Mitsubishi Chemical Co., Ltd., now jER (registered trademark) series), EPPN201, EPPN202 ( The above are phenol novolak type epoxy compounds such as Nippon Chemical Co., Ltd.; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (The above are Japanese chemical drugs) (share) system, Epikote 180S75 (Japan epoxy resin (shares) (now Mitsubishi Chemical (shares), now jER (registered trademark) series) a cresol novolak type epoxy compound; a naphthalene type epoxy compound such as V8000-C7 (made by DIC); DENACOL EX-252 (manufactured by Changkang Contax), CY175, CY177 , CY179, Araldite CY-182, Araldite CY-192, AralditeCY-184 (above is made by BASF), EPICLON 200, EPICLON 400 (above, DIC), Epikote 871, Epikote 872 (above is Japanese epoxy resin) (now Mitsubishi Chemical (share), now An alicyclic epoxy compound such as ED-5661, ED-5662 (above, manufactured by Celanese coating); DENACOL EX-611, DENACOL EX-612, DENACOL EX- 614, DENACOL EX-622, DENACOL EX-411, DENACOL EX-512, DENACOL EX-522, DENACOL EX-421, DENACOL EX-313, DENACOL EX-314, DENACOL EX-312 (above is Changtai Contes) An aliphatic polyglycidyl ether compound.

The melamine derivative, the benzoguanamine derivative or the glycol urea of the group in which the hydrogen atom of the amine group is substituted by a methylol group, an alkoxymethyl group or both thereof may be exemplified per one triazine ring. The methoxymethyl group is an average of 3.7 substituted MX-750, and the methoxymethyl group per one triazine ring is an average of 5.8 substituted MW-30 (above (three) and chemical); Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc. methoxymethylated melamine; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Methoxymethylated butoxymethylated melamine of Cymel 253, Cymel 254, etc.; butoxymethylated melamine of Cymel 506, Cymel 508, etc.; such as methoxymethylation of carboxyl group of Cymel 1141 Butyloxymethylated melamine; methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; methoxymethylated butoxymethylated benzopyrene such as Cymel 1123-10 amine; a butoxymethylated benzoguanamine such as Cymel 1128; a methoxymethylated ethoxymethylated benzoguanamine containing a carboxyl group such as Cymel 1125-80; a butoxymethyl group such as Cymel 1170 Glycol urea; such as hydroxymethylated glycol urea of Cymel 1172 (above is Mitsui Cyanamid (now Cytec Industries)) and the like.

The polyamidiamine precursor contained in the composition of the present invention is also a subject of the present invention, for example, a tetracarboxylic dianhydride represented by the formula (20) and three diamines, which may also be obtained by the formula (21) The diamine, the diamine represented by the formula (22) and the diamine represented by the formula (23) are reacted.

In the formulae (20) to (23), R ¹ to R ^{24 have} the same meanings as described above.

In the above reaction, the mass M ^{1 of the} diamine represented by the formula (21), the mass M ^{2 of the} diamine represented by the formula (22), and the mass M ^{3 of the} diamine represented by the formula (23) preferably satisfy the M. ² / (M ¹ + M ³ ) = 70/30 to 99/1, more preferably 75/25 to 95/5.

Further, M ¹ and M ³ preferably satisfy M ¹ /M ³ =10/90 to 90/10, more preferably M ¹ /M ³ =40/60 to 60/40.

In the above reaction, the addition ratio of the carboxylic dianhydride component represented by the formula (20) to the total diamine (diamine represented by the formulae (21) to (23)) is usually 1 mol per carboxylic acid dianhydride. It is about 0.8~1.2 mu of total diamine, preferably about 0.95~1.05 mol.

The solvent used for the reaction of the above polyimide precursor can dissolve the raw material compound, and is not particularly limited as long as it does not inhibit the reaction.

Specific examples thereof include N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone. , hexamethylphosphonium amide, dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, 1,2-dimethoxyethane-bis (2-A) An aprotic solvent such as oxyethyl)ether, tetrahydrofuran, 1,4-dioxane, methylpyridine, pyridine, acetone, chloroform, toluene or xylene, and phenol, o-cresol, m-cresol, A protic solvent such as p-cresol, o-chlorophenol, m-chlorophenol or p-chlorophenol. These solvents may be used alone or in combination of two or more.

The reaction temperature may be appropriately set in the range from the melting point of the solvent to the boiling point of the solvent, and is usually about -20 to 100 ° C, preferably about 15 to 80 ° C. Further, the reaction time of the polymerization is usually about 1 to 72 hours.

Further, the ruthenium imidized polymer contained in the composition of the present invention is also a subject of the present invention, and can be obtained, for example, by dehydration ring closure (oxime imidization) of the above polyimine precursor. The method of dehydration ring closure may take any one of dehydration ring closure by heating (thermal enthalpy imidization) and dehydration ring closure by a catalyst.

The heating temperature by the dehydration ring of heating is not particularly limited as long as the ring closure reaction can be carried out, but is usually 100 to 450 ° C, preferably 100 to 420 ° C.

Further, it is carried out by a dehydration ring closure of a catalyst, for example, in the presence of a base and an acid. The temperature for performing the dehydration ring closure by the catalyst can be selected as long as the reaction can be carried out.

The tetracarboxylic dianhydride and the diamine used for the above reaction may be commercially available or may be synthesized by a known method.

The composition (varnish) described above is applied onto a substrate, and by evaporating the solvent, a film suitable for the substrate material can be formed on the substrate.

The coating method of the varnish is not particularly limited, and examples thereof include a casting coating method, a spin coating method, a knife coating method, a dip coating method, a roll coating method, a bar coating method, and a die coating method. Method, inkjet method, printing method (embossing, gravure, lithography, screen printing, etc.).

Further, examples of the substrate for applying the varnish include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose). , ABS, AS, decene-based resin, etc.), metal, wood, paper, glass, slate, etc.

The solvent of the varnish can be evaporated, for example, by using a hot plate or an oven under an appropriate environment, that is, an inert gas such as air or nitrogen, or a vacuum. Thereby, a film having a uniform film formation surface can be obtained.

The firing temperature is usually from 100 to 450 ° C, preferably from 100 to 420 ° C. At this time, by making it exhibit a higher uniform film forming property, or making it on the substrate For the purpose of performing the reaction, a temperature change of two or more stages may be attached.

The film thickness of the cured film is not particularly limited, but is preferably 1 to 50 μm, more preferably 5 to 40 μm, when used as a substrate film (substrate material) such as a flexible display.

The method of changing the film thickness may, for example, be a method of changing the concentration of the solid content in the varnish or changing the amount of the solution on the substrate at the time of coating.

The cured film obtained by the method described above is expected to be used as, for example, a liquid crystal display, an organic EL illumination, an electronic paper, etc. due to appropriate flexibility, excellent heat resistance, appropriate linear expansion coefficient, and high transparency. The use of substrate materials in the field of such devices requiring such characteristics.

[Examples]

The present invention will be more specifically described by the following examples, but the invention is not limited to the examples described below.

[1] Abbreviation used in the examples

PDA: p-phenylenediamine (Tokyo Chemical Industry Co., Ltd.)

APAB: 2-(3-Aminophenyl)-5-aminobenzimidazole (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.) (Formula (24))

TFMB: 2,2'-bis(trifluoromethyl)benzidine (manufactured by Tokyo Chemical Industry Co., Ltd.) (Formula (25))

BAPPS: bis[4-(3-aminophenoxy)phenyl]indole (Tokyo Chemical Industry Co., Ltd.) System) (Formula (26))

BAPS: bis(3-aminophenyl)anthracene (Tokyo Chemical Industry Co., Ltd.) (Formula (27))

NMP: N-methyl-2-pyrrolidone

[2] Determination of weight average molecular weight (hereinafter also referred to as Mw) and molecular weight distribution of polymer

The gel permeation chromatography (GPC) apparatus used for the measurement of the Mw and molecular weight distribution of the polymer and its conditions are as follows. Further, Mw is a value converted to polystyrene.

GPC: ChromNav, JASCO

Pipe column: Shodex [registered trademark] SB803HQ and SB804HQ by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Solvent: N,N-dimethylformamide (0.9 mL/min)

Detector: RI

[3] Synthesis of polyimine precursor acid and manufacture of varnish [Example 1]

After TFMB 16 g (0.005 mol), APAB 1.4 g (0.0006 mol), and PDA 0.63 g (0.0006 mol) were dissolved in NMP 170 g, and CBDA (manufactured by Tokyo Chemical Industry Co., Ltd.) 12 g (0.061 mol) was added. The reaction was carried out at 23 ° C for 24 hours under a nitrogen atmosphere to obtain a polymer (Mw 38, 700 molecular weight distribution 2.1)

The obtained polymer solution was directly used as the varnish of Example 1 in the production of a cured film (solid content: 15%) described later.

[Comparative Example 1]

BAPPS 4.13 g (0.0095 mol) was dissolved in NMP 14.0 g, and CBDA 1.87 g (0.0095 mol) was added, and then reacted at 23 ° C for 24 hours under nitrogen to obtain a polymer (Mw 19,800 molecular weight distribution 2.1). .

The obtained polymer solution was directly used as a varnish of Comparative Example 1 in the production of a cured film (solid content: 30%) described later.

[Comparative Example 2]

BAPS 3.35 g (0.013 mol) was dissolved in NMP 14.0 g, and CBDA 2.65 g (0.014 mol) was added, and then reacted at 23 ° C for 24 hours in a nitrogen atmosphere to obtain a polymer (Mw 13,600 molecular weight distribution 3.1). .

The obtained polymer solution was directly used as a varnish of Comparative Example 2 in the production of a cured film (solid content: 30%) described later.

[4] Manufacture and evaluation of hardened film <Manufacture of cured film and evaluation of film thickness>

The varnishes produced in Example 1 and Comparative Examples 1 and 2 were applied to a glass substrate by a bar coater, and under reduced pressure, at 110 ° C for 10 minutes, at 230 ° C for 30 minutes, at 300 ° C for 30 minutes. The film was heated at 350 ° C for 120 minutes to obtain a cured film.

The film thickness of the obtained cured film was measured using a contact film thickness measuring instrument (Dektak 3ST manufactured by ULVAC).

<Evaluation of self-supporting>

The glass substrate on which the cured film was formed was placed in pure water at 70 ° C to peel off the cured film. The peeled cured film was evaluated for self-support by bending.

<Measurement of heat resistance>

A small piece of about 5 mg by weight was cut out from the peeled cured film, and heat resistance was evaluated by heating the small piece (5 ° C per minute from 50 ° C to 500 ° C) to measure the 5% mass reduction. For the evaluation, TG/DTA-2000SA (manufactured by Bruker AXS Co., Ltd.) was used.

<Transmission rate measurement>

The transmittance of the cured film of the glass-attached substrate produced above was measured using a self-recording spectrophotometer UV-3100PC manufactured by Shimadzu Corporation.

<linear expansion coefficient>

A strip of 20 mm × 5 mm was cut out from the peeled cured film, and TMA-4000SA (manufactured by Bruker AXS Co., Ltd.) was used for the strip, and the temperature was 5 ° C / min from 50 ° C to 150 ° C. After heating and cooling, the coefficient of linear expansion was again measured by heating from 50 ° C to 400 ° C. Further, since the cured film of Comparative Example 2 did not have sufficient self-supporting property, the coefficient of linear expansion could not be measured.

The above evaluation results are shown in Table 1. Further, the transmittance is a value of a wavelength of 400 nm.

As shown in Table 1, the cured film obtained from the varnish of Example 1 was obtained not only having a low coefficient of linear expansion but also excellent transparency and self-support as compared with those obtained from the varnishes produced in Comparative Examples 1 and 2. The result of sex and heat resistance.

Claims (13)

A composition for a heat resistant substrate comprising a polyimine precursor selected from the group consisting of a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3) And at least one of the group consisting of the ruthenium imidized polymer and an organic solvent, In the formula (1) to the formula (3), X ¹ represents a tetravalent group represented by the formula (4). (In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms; and Y ¹ represents a formula (5). The basis of the price of 2 (In the formula (5), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. ); Y ² represents a divalent base represented by the formula (6), [In the formula (6), R ¹³ to R ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms; (However, at least two of R ¹³ to R ²⁰ represent a perfluoroalkyl group having 1 to 6 carbon atoms); Y ³ represents a divalent group represented by the formula (7). (In the formula (7), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. )}. The composition for a heat resistant substrate according to claim 1, wherein the Y ¹ system represents a divalent group represented by the formula (8). (In the formula (8), R ⁵ to R ¹² represent the same meanings as described above). The composition for a heat resistant substrate according to claim 1 or 2, wherein the R ⁵ represents a hydrogen atom, and each of R ⁶ to R ¹² independently represents a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms. The composition for a heat resistant substrate according to any one of claims 1 to 3, wherein the Y ² system represents a divalent group represented by the formula (9). (In the formula (9), R ¹³ to R ²⁰ represent the same meanings as described above). The heat resistant substrate composition according to any one of claims 1 to 4, wherein each of R ¹³ to R ²⁰ independently represents a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms. The composition for a heat resistant substrate according to any one of claims 1 to 5, wherein the Y ³ system represents a divalent group represented by the formula (10). (In the formula (10), R ²¹ to R ²⁴ represent the same meanings as described above). The composition for a heat resistant substrate according to any one of claims 1 to 6, wherein each of R ²¹ to R ²⁴ independently represents a hydrogen atom or a perfluoroalkyl group having 1 to 6 carbon atoms. The composition for a heat resistant substrate according to any one of claims 1 to 7, wherein the R ¹ to R ⁴ represent a hydrogen atom, a methyl group or a trifluoromethyl group. A film obtained by applying the composition for a heat resistant substrate according to any one of claims 1 to 8 and heating the film. A substrate material formed by the film of claim 9. The substrate material described in claim 10 is used for a display substrate. A polyimine precursor comprising a structural unit represented by the formula (1), a structural unit represented by the formula (2), and a structural unit represented by the formula (3). In the formulas (1) to (3), X ¹ represents a tetravalent group represented by the formula (4). (In the formula (4), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a perfluoroalkyl group having 1 to 6 carbon atoms; and Y ¹ represents a formula (5). The basis of the price of 2 (In the formula (5), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. ); Y ² represents a divalent base represented by the formula (6), [In the formula (6), R ¹³ to R ²⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms; (However, at least two of R ¹³ to R ²⁰ represent a perfluoroalkyl group having 1 to 6 carbon atoms); Y ³ represents a divalent group represented by the formula (7). (In the formula (7), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms or an aromatic group having 6 to 14 carbon atoms. )}. A quinone imidized polymer of the polyimine precursor described in claim 12.