TWI620792B - Resin composition for display substrate, resin thin film for display substrate and production method for resin thin film for display substrate - Google Patents

Abstract

An object of the present invention is to provide a diamine having versatility and a versatility of acid dianhydride, which has high heat resistance, moderate flexibility, and moderate linear expansion coefficient which can withstand the manufacturing process of a display. A resin composition for a display substrate of a resin film.

The solution is a resin composition for a display substrate, which comprises a polyglycine having a weight average molecular weight of 5,000 or more in three structural units represented by the formula (1-1) in a total of at least 50 mol%.

Wherein Ar ¹ represents a divalent group represented by any one of the formulae (2) to (4), Ar ² represents a divalent group represented by the formula (5), and Ar ³ represents a divalent group represented by the formula (6) , Ar ⁴ represents a tetravalent group represented by the formula (7) or (8), and n ¹ to n ³ represent the number of each structural unit, and satisfy n ¹ /(n ² +n ³ )=2.0 to 9.0 and n ² / n ³ = 0.1~10].

Description

Resin composition for display substrate, resin film for display substrate, and method for producing resin film for display substrate

The present invention relates to a resin composition for a display substrate, a resin film for a display substrate, and a method for producing a resin film for a display substrate.

In recent years, in the field of display devices such as organic electroluminescence displays and liquid crystal displays, in addition to high definition, demands for weight reduction, flexibility, and the like have been further enhanced. Under such circumstances, it is known that a polyimide resin which is easy to manufacture and has high heat resistance is attracting attention as a substrate material for a display for glass replacement.

However, in order to use polyimide as the material of the display substrate, it is necessary to have a linear expansion coefficient (about 5 to 15 ppm/K) which is as small as glass, and most polyimine has a linear expansion of about 60 to 80 ppm/K. The coefficient, therefore the majority of the polyimides are not suitable for the substrate material of the display.

That is, you want to use the active matrix drive panel as a high-precision A fine display, and an active matrix layer including a thin film active device is formed in addition to the matrix-shaped pixel electrode, which requires not only high temperature processing of 200 ° C or higher but also correct positional alignment. However, polyimine is inferior to glass in terms of linear expansion characteristics (linear expansion coefficient), and therefore shrinks or swells more greatly than a glass substrate at a high temperature, so when polyimide is used as a substrate material, it is used in the manufacturing process of the display. It is often difficult to maintain high dimensional stability.

Therefore, in order to utilize the heat resistance of polyimine and to achieve suitable linear expansion characteristics, it is necessary to have a more suitable molecular design.

In this regard, a polyimide film having a low coefficient of linear expansion in view of the above facts has been proposed (Patent Document 1). However, in this proposed technique, the lack of versatility of acid dianhydride is used as a raw material of polyimine, and thus the obtained polyimide film is expensive, and as a result, the price of the display itself using the film is expected to become high. .

On the other hand, various reports have been reported on the use of polybenzine produced by using biphenyltetracarboxylic dianhydride or pyromellitic anhydride having a general-purpose acid anhydride (Patent Documents 2 to 4 and Non-Patent Document 1). The polyimine produced by the former biphenyltetracarboxylic dianhydride has a problem that the linear expansion coefficient in the high temperature region (250 ° C to 400 ° C) necessary for the manufacturing process is increased, and the latter is used. In the case of a combination with a p-phenylenediamine having a general diamine, the flexibility of the obtained polyimine is lowered.

Thus, a polylysine which is suitable for producing a polyimine film obtained from a versatile diamine and a general-purpose acid dianhydride and having characteristics necessary for a display substrate has not been specifically known, or contains Its resin composition.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2008/047591

[Patent Document 2] International Publication No. 2011/151898

[Patent Document 3] International Publication No. 2012/033213

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-202729

[Non-patent literature]

[Non-Patent Document 1] Journal of Applied Polymer Science, Vol. 62, 2303-2310 (1996)

The present invention has been made in view of such circumstances, and an object thereof is to provide a diamine which is versatile and a pharmaceutically acceptable acid dianhydride, which has high heat resistance and moderate flexibility which can withstand the manufacturing process of a display. And a resin composition for a display substrate of a resin film having a moderate linear expansion coefficient, particularly a moderate linear expansion coefficient at around 400 °C.

Further, the moderate softness referred to herein means a degree of softness which is self-supporting and which does not break even if it is bent at 90 degrees. Further, a moderate coefficient of linear expansion means, for example, a linear expansion coefficient (about 5 to 15 ppm/K) which is equal to or lower than the glass of the substrate when the substrate is glass.

As a result of repeated efforts by the present inventors to achieve the above object, it has been found that by containing benzenetetracarboxylic dianhydride, phenylenediamine, 9,9-bis(4-aminophenyl)anthracene, and 4,4' - a composition of polylysine derived from bis(4-aminophenoxy)biphenyl to obtain a resin film having high heat resistance, moderate flexibility, and a moderate coefficient of linear expansion necessary for a display substrate. The present invention has been completed.

That is, the present invention provides:

A resin composition for a display substrate comprising a polyglycine having a weight average molecular weight of 5,000 or more and three structural units represented by the formula (1-1) in a total amount of at least 50 mol%. Wherein Ar ¹ represents a divalent group represented by any one of the formulae (2) to (4), Ar ² represents a divalent group represented by the formula (5), and Ar ³ represents a divalent group represented by the formula (6) , Ar ⁴ represents a tetravalent group represented by the formula (7) or (8), and n ¹ to n ³ represent the number of each structural unit, and satisfy n ¹ /(n ² +n ³ )=2.0 to 9.0 and n ² / n ³ = 0.1~10].

2. The resin composition for a display substrate according to 1, wherein the polyamic acid is represented by the formula (1-2) In the formula (1-2), X ¹ represents a monovalent group represented by the formula (9) or (10), and X ² represents a monovalent group represented by the formula (11) or (12), and Ar ¹ to Ar ⁴ and n ¹ to n ³ represents the same meaning as described above, and X ₁ and X ₂ are independently bonded arbitrarily to the three structural units represented by the formula (1-1); [In the formulae (9) to (12), Y ¹ represents a divalent group represented by any one of the formulae (13) to (15), Y ² represents a monovalent group represented by the formula (16), and Ar ⁵ represents the above formula. (2) The divalent group represented by any one of (6), and Ar ⁴ represents a tetravalent group represented by the above formula (7) or (8); (In the formulae (13) to (16), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a monovalent group represented by the formula (17) or (18), q Indicates the number of Z bonded to the benzene ring and represents an integer from 1 to 3.

(In the formulae (17) and (18), R ⁵ to R ⁸ each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms))]}.

A resin film for a display substrate produced by using a resin composition for a display substrate as described in 1 or 2.

A resin film for a display substrate, which is obtained by applying a resin composition for a display substrate of 1 or 2 to a substrate, and heating at 50 ° C to 100 ° C for 5 minutes to 2 hours at a temperature exceeding 100 ° C. Heating at 200 ° C for 5 minutes to 2 hours, heating at more than 200 ° C ~ 375 ° C for 5 minutes to 2 hours, It is made by heating over 375 ° C ~ 450 ° C for 30 minutes ~ 4 hours.

An image display device comprising a resin film for a display substrate such as 3 or 4.

A method for producing a resin film for a display substrate, which comprises using a resin composition for a display substrate as described in 1 or 2.

A method for producing a resin film for a display substrate, characterized in that a resin composition for a display substrate of 1 or 2 is applied onto a substrate, and heated at 50 to 100 ° C for 5 minutes to 2 hours, respectively. Heating from 100 ° C to 200 ° C for 5 minutes to 2 hours, heating at more than 200 ° C to 375 ° C for 5 minutes to 2 hours, and heating at more than 375 ° C to 450 ° C for 30 minutes to 4 hours.

A method of producing an image display device, characterized in that a resin film for a display substrate such as 3 or 4 is used.

A polyaminic acid containing at least 50 mol% of the total of three structural units represented by the formula (1-1), and having a weight average molecular weight of 5,000 or more. Wherein Ar ¹ represents a divalent group represented by any one of the formulae (2) to (4), Ar ² represents a divalent group represented by the formula (5), and Ar ³ represents a divalent group represented by the formula (6) , Ar ⁴ represents a tetravalent group represented by the formula (7) or (8), and n ¹ to n ³ represent the number of each structural unit, and satisfy n ¹ /(n ² +n ³ )=2.0 to 9.0 and n ² / n ³ = 0.1~10].

10. Polyurethane according to 9, which is represented by formula (1-2) In the formula (1-2), X ¹ represents a monovalent group represented by the formula (9) or (10), and X ² represents a monovalent group represented by the formula (11) or (12), and Ar ¹ to Ar ⁴ and n ¹ ~ n ³ , which means the same meaning as described above. X ₁ and X ₂ are independently bonded to the three structural units represented by the formula (1-1).

[In the formulae (9) to (12), Y ¹ represents a divalent group represented by any one of the formulae (13) to (15), Y ² represents a monovalent group represented by the formula (16), and Ar ⁵ represents the above formula. (2) The divalent group represented by any one of (6), and Ar ⁴ represents a tetravalent group represented by the above formula (7) or (8); (In the formulae (13) to (16), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a monovalent group represented by the formula (17) or (18), q Represents the number of Z bonded to the benzene ring, and represents an integer from 1 to 3; (In the formulae (17) and (18), R ⁵ to R ⁸ each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms))]}.

The resin composition for a display substrate of the present invention can be produced from a general-purpose acid dianhydride and a versatile diamine, and by using the resin composition, it can be large-area and reproducible by a wet process. A resin thin film having high heat resistance, moderate flexibility, and moderate linear expansion coefficient, especially a moderate linear expansion coefficient around 400 ° C is obtained. membrane.

Therefore, by using the resin composition for a display substrate of the present invention, not only can the weight of the display be reduced or densified, but also the cost of the raw material can be reduced or the manufacturing efficiency can be reduced.

Hereinafter, the present invention will be described in detail.

The resin composition for a display substrate of the present invention comprises a polyglycine having a weight average molecular weight of 5,000 or more in three structural units represented by the formula (1-1) in a total of at least 50 mol%.

In the formula (1-1), Ar ¹ represents a divalent group represented by any one of the formulae (2) to (4), Ar ² represents a divalent group represented by the formula (5), and Ar ³ represents a formula (6). The 2 price base. In particular, when a resin film having high flexibility is obtained in consideration of reproducibility, Ar ^{1 is} preferably a group represented by the formula (2) or (3), and most preferably a group represented by the formula (2).

In the formula (1-1), Ar ⁴ represents a tetravalent group represented by the formula (7) or (8). In particular, when a resin film having high flexibility is obtained in consideration of reproducibility, Ar ^{4 is} most preferably a group represented by the formula (7).

In the formula (1-1), n ¹ to n ³ represent the number of each structural unit, and satisfy n ¹ /(n ² +n ³ )=2.0 to 9.0 and n ² /n ³ =0.1 to 10.

When a resin film having a moderate linear expansion coefficient is obtained with good reproducibility, n ¹ to n ³ preferably satisfy n ¹ /(n ² +n ³ )=2.1 to 7.0, more preferably 2.3 to 7.0. 5.0. On the other hand, n ² and n ³ preferably satisfy n ² /n ³ = 0.2 to 5.0, more preferably 0.5 to 2.0.

In the present invention, by using a polylysine represented by the formula (1-2) having an unsaturated bond at both terminals, it is possible to obtain a higher reproducibility. Heat resistant resin film.

(In the formula, Ar ¹ to Ar ⁴ and n ¹ to n ³ represent the same meanings as described above).

In the formula (1-2), X ¹ represents a monovalent group represented by the formula (9) or (10), and X ² represents a monovalent group represented by the formula (11) or (12). Further, X ₁ and X ₂ are independently bonded to the three structural units represented by the formula (1-1).

(In the formula, Ar ⁵ represents a divalent group represented by any one of the above formulas (2) to (6), and Ar ⁴ represents the same meaning as described above).

In the formulae (9) to (12), Y ¹ represents a divalent group represented by any one of the formulae (13) to (15), and Y ² represents a monovalent group represented by the formula (16).

In the formulae (13) and (16), Z represents a monovalent group represented by the formula (17) or (18).

In the formulae (17) and (18), R ⁵ to R ⁸ each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms.

Examples of the aryl group having 6 to 20 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, a 2-phenanthryl group, and 3 - phenanthryl, 4-phenanthryl, 9-phenanthryl and the like.

When considering the solubility of the polyamic acid in the organic solvent, R ⁵ to R ^{8 are} preferably a hydrogen atom or an aryl group having 14 or less carbon atoms, more preferably a hydrogen atom or an aryl group having 10 or less carbon atoms, More preferably, it is a hydrogen atom or a phenyl group. Further, one of R ⁵ to R ⁷ is preferably a hydrogen atom, and more preferably two is a hydrogen atom.

In the formulae (13) and (16), q represents the number of Z bonded to the benzene ring, and is an integer of 1 to 3, preferably 1 or 2. Furthermore, when q is 2 or more, a plurality of Z's may be the same or different.

In the formulae (14) and (15), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. S-butyl, t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl a straight or branched chain alkyl group having 1 to 20 carbon atoms, a n-fluorenyl group, an n-fluorenyl group, etc.; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group And a cycloalkyl group having a carbon number of 3 to 20, such as a cyclodecyl group, a cyclodecyl group, a dicyclobutyl group, a dicyclopentyl group, a bicyclohexyl group, a bicycloheptyl group, a bicyclooctyl group, a bicyclononyl group or a bicyclononyl group.

When considering the improvement of the solubility of the polyamic acid in the organic solvent, R ¹ to R ^{4 are} preferably a hydrogen atom or an alkyl group having 10 or less carbon atoms, more preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, More preferably, it is a hydrogen atom or a methyl group. Further, it is preferred that each of R ¹ and R ² and R ³ and R ⁴ is a hydrogen atom.

Further, in the present specification, the polyamic acid containing the three structural units represented by the formula (1-1) and the polylysine represented by the formula (1-2) mean that the polymer chain contains the formula (a). The structural unit represented by the formula, the structural unit represented by the formula (b), and the structural unit represented by the formula (c) are 50 mol% or more in total, and the structural units are in any order (these units may also be Poly-proline which contains other constituent units). Therefore, in the present specification, in order to clarify the meaning, each structural unit in the formulas (1-1) and (1-2) in the present claim is different from the repeating unit in that the keying key is not crossed.

Further, such other structural units may be exemplified by 2-methyl-1,4-phenylenediamine, 5-methyl-1,3-phenylenediamine, and 4-methyl-1,3-phenylenediamine. , benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,3'-dimethylbenzidine, 4,4'-diphenyl ether, 4,4 '-Diaminobenzimidoximine, 5-amino-2-(3-aminophenyl)-1H-benzimidazole, etc., and 2,3,6,7-naphthalenetetracarboxylic acid Anhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-benzophenone tetracarboxylate Anhydride, 1,4-bis(3,4-dicarboxyl) A structure in which an acid dianhydride such as phenoxy)phthalic anhydride is reacted and derived, but is not limited thereto.

(In the formula, Ar ¹ to Ar ⁴ represent the same meaning as described above).

The polyamic acid used in the present invention contains at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, and more preferably the three structural units represented by the formula (1-1). Preferably, it is at least 80% by mole, and even more preferably at least 90% by mole. By using such a polyamic acid, a resin film having characteristics suitable for a display substrate can be obtained with good reproducibility.

The polyamic acid used in the present invention may contain other structural units in addition to the three structural units represented by the formula (1-1) (structural units represented by the formulas (a) to (c)), and the content of the structural unit Must be less than 50% by mole, preferably less than 40% by mole, more preferably less than 30% by mole, more preferably less than 20% by mole, and even more preferably less than 10% ear%.

Polydecylamine containing three structural units represented by formula (1-1) The acid can be obtained by reacting a diamine represented by the formula (19) to (21) with an acid dianhydride represented by the formula (22).

(In the formula, Ar ¹ and Ar ⁴ represent the same meanings as described above).

The diamine represented by the formula (19) to (21) and the acid dianhydride represented by the formula (22) may be commercially available or may be synthesized by a known method.

The diamine represented by the formula (19) includes p-phenylenediamine, m-phenylenediamine or o-phenylenediamine.

The acid dianhydride represented by the formula (22) may, for example, be 1,2,3,4-benzenetetracarboxylic dianhydride or 1,2,4,5-benzenetetracarboxylic dianhydride (benzenetetracarboxylic anhydride).

Further, the polylysine represented by the formula (1-2) of the present invention can be represented by the diamine represented by the formulae (19) to (21), the acid dianhydride represented by the formula (22), and the formula (23). An acid anhydride represented by any one of ~(25) and/or an amine represented by the formula (26) is obtained by a reaction.

(wherein R ¹ to R ⁴ , Z and q represent the same meaning as described above.)

The acid anhydride represented by the formula (23) to (25) and the amine represented by the formula (26) may be commercially available or may be synthesized by a known method.

Examples of the acid anhydride represented by the formula (23) include 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 4-phenylethynylphthalic anhydride, and 4-ethynylphthalic acid. An acid anhydride, but is not limited thereto.

The acid anhydride represented by the formula (24) includes, but is not limited to, 5-northene-2,3-dicarboxylic anhydride and methyl-5-nordecene-2,3-dicarboxylic anhydride.

The acid anhydride represented by the formula (25) may, for example, be maleic anhydride or citraconic anhydride, but is not limited thereto.

The amine represented by the formula (26) may, for example, be 2-ethynylaniline, 3-ethynylaniline or 4-ethynylaniline, but is not limited thereto.

In the above reaction, the diamine represented by the formulae (19) to (21), the amine represented by the formula (26) (hereinafter referred to as an amine component), the acid dianhydride represented by the formula (22), and the formula (23) to (25) The feed ratio (molar ratio) of the acid anhydride (hereinafter referred to as the acid anhydride component) is appropriately set in consideration of the molecular weight of the polyamic acid, but the acid anhydride component is usually 0.6 with respect to the amine component 1. ~1.4 or so, preferably about 0.8~1.2.

Further, regarding the feed ratio (mole ratio) of various diamines represented by the formulas (19) to (21), the molar number (m ² ) of the diamine represented by the formula (20) and the formula (21) are represented. When the molar number of the diamines (m ³ ) is 1, the molar number (m ¹ ) of the diamine represented by the formula (19) is usually from about 2.0 to 9.0, preferably from 2.1 to 7.0, more preferably 2.3. ~5.0. That is, m ¹ to m ³ is usually m ¹ /(m ² +m ³ )=2.0 to 9.0, preferably 2.1 to 7.0, more preferably 2.3 to 5.0.

On the other hand, regarding the feed ratio (mole ratio) of various diamines represented by the formulas (20) to (21), the diamine represented by the formula (20) with respect to the diamine 1 represented by the formula (21) It can be about 0.1 to 10, preferably 0.2 to 5.0, more preferably 0.5 to 2.0. That is, m ² to m ³ is usually m ² /m ³ = 0.1 to 10, preferably 0.2 to 5.0, more preferably 0.5 to 2.0.

The above reaction is preferably carried out in a solvent, and when a solvent is used, various solvents can be used as long as they do not adversely affect the reaction.

Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and N. N-dimethylacetamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethyl Propylamine, 3-propoxy-N,N-dimethylpropanamide, 3-isopropoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-di Methyl acrylamide, 3-sec-butoxy-N,N-dimethylpropanamide, 3-tert-butoxy-N,N-dimethylpropionamide, γ -butyrolactone, etc. Protonic solvent, etc. These may be used alone or in combination of two or more.

The reaction temperature may be appropriately set within a range from the melting point of the solvent to the boiling point of the solvent to be used, and is usually about 0 to 100 ° C. However, in order to prevent the imidization of the obtained polylysine, the polyamine unit is maintained. It The high content is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and even more preferably about 0 to 50 ° C.

The reaction time depends on the reaction temperature or the reactivity of the starting materials, and cannot be generalized, and is usually about 1 to 100 hours.

By the method described above, a reaction solution containing the desired polylysine can be obtained.

In the present invention, the reaction solution is usually filtered, and the filtrate is directly or diluted or concentrated to be used as a resin composition (varnish) for a display substrate. In this manner, it is possible to reduce not only the incorporation of impurities which can deteriorate the heat resistance, the flexibility, or the linear expansion property of the obtained resin film, but also the composition can be efficiently obtained.

The solvent to be used for the dilution or concentration is not particularly limited, and examples thereof include the same as the specific examples of the reaction solvent of the above reaction, and these may be used alone or in combination of two or more.

Among these, in view of obtaining a resin film having high flatness with good reproducibility, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl- are particularly preferable. 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone.

Further, in the present invention, the reaction solution may be post-treated in accordance with a general method, and the varnish obtained by dissolving or dispersing the isolated polylysine in a solvent may be used as a display. The substrate is used as a resin composition. In this case, in consideration of obtaining a resin film having high flatness with good reproducibility, polyphthalic acid is preferably dissolved in a solvent. The solvent to be used for the dissolution or dispersion is not particularly limited, and examples thereof include the above reaction. Specific examples of the reaction solvent are the same, and these may be used alone or in combination of two or more.

The concentration of the polyamic acid relative to the total mass of the varnish is appropriately set in consideration of the thickness of the film to be produced or the viscosity of the varnish, but is usually about 0.5 to 30% by mass, preferably about 5 to 25% by mass.

In addition, although the viscosity of the varnish is appropriately set in consideration of the thickness of the film to be produced, the resin film having a thickness of about 5 to 50 μm is preferably used for reproducibility, and is usually 500 to 50,000 mPa at 25 ° C. s or so, preferably 1,000 to 20,000 mPa. s or so.

The resin composition for a display substrate of the present invention may contain a crosslinking agent (hereinafter also referred to as a crosslinkable compound). The content of the crosslinking agent is usually about 20 parts by mass or less based on 100 parts by mass of the polyamic acid.

Specific examples of the crosslinkable compound are listed below, 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, and Celloxide 3000 (above, manufactured by Daicel Chemical Industries Co., Ltd.). Epoxy compound having a cyclohexene structure; bisphenol A type such as Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above, Japan Epoxy Resin) Epoxy compound; bisphenol F type epoxy compound such as Epikote 807 (made by Japan Epoxy Resin Co., Ltd.); Epikote 152, Epikote 154 (above, Japan Epoxy Resin Co., Ltd.), EPPN201, EPPN202 (above, Nipponization) Phenolic novolac type epoxy compounds such as medicinal (stock) system; ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (above, Nippon Kayaku Co., Ltd.) , a cresol novolak type epoxy compound such as Epikote 180S75 (made by Japan Epoxy Resin Co., Ltd.); a naphthalene type epoxy compound such as V8000-C7 (made by DIC); and Denacol EX-252 (Nagase ChemteX (share) ), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, BASF), Epiclon 200, Epiclon 400 (above, DIC), Epikote 871, Epicyclic epoxides such as Epikote 872 (above, manufactured by Japan Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (above, manufactured by Celanese Coating Co., Ltd.); 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, Nagase ChemteX ( An aliphatic polyglycidyl ether compound such as a compound).

A melamine derivative, a benzoguanamine derivative or an acetylene urea which is a group in which a hydrogen atom having an amine group is substituted with a methylol group, an alkoxymethyl group or both, may be exemplified by an average of 3.7 per triazine ring. Methoxy-substituted MX-750, MW-30 (above, (three) and Chemical) substituted with an average of 5.8 methoxymethyl groups per ring; Cymel 300, Cymel 301 Methoxymethylated melamine of Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc.; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254, etc. methoxymethylated butoxymethylated melamine; Cymel 506, Cymel 508, etc. butoxymethylated melamine; such as Cymel 1141 containing carboxyl Methoxymethylated isobutoxymethylated melamine; methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123; methoxymethylated butyl such as Cymel 1123-10 An oxymethylated benzoguanamine; a butoxymethylated benzoguanamine such as Cymel 1128; a methoxymethylated ethoxymethylated benzoguanamine containing a carboxyl group such as Cymel 1125-80 ; such as Cymel 1170 butoxymethylated acetylene urea; such as Cymel 1172 hydroxymethylated acetylene urea (above, Mitsui Cyanamid Co., Ltd.) and the like.

By applying the resin composition for a display substrate of the present invention described above to a substrate and heating it, a resin composed of a polyimine having high heat resistance, moderate flexibility, and a moderate coefficient of linear expansion can be obtained. film.

The base (substrate) may, for example, be a plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine, triethylenesulfonyl cellulose, ABS, AS, norbornene). A resin or the like, a metal, wood, paper, glass, a flat plate or the like is preferably the glass substrate from which the obtained resin film exhibits good peelability.

The method of coating is not particularly limited, and examples thereof include a cast 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.).

The heating temperature is preferably 450 ° C or less. Above 450 ° C, There may be cases where the obtained resin film becomes brittle and a resin film suitable for the use of the display substrate cannot be obtained.

Further, in consideration of obtaining a resin film having high heat resistance and a low coefficient of linear expansion, it is preferred to directly heat the applied resin composition at 50 ° C to 100 ° C for 5 minutes to 2 hours. The ground rises and finally heats over 375 ° C ~ 450 ° C for 30 minutes ~ 4 hours.

Particularly preferably, the coated resin composition is heated at 50 ° C to 100 ° C for 5 minutes to 2 hours, then heated at more than 100 ° C to 200 ° C for 5 minutes to 2 hours, followed by heating at more than 200 ° C to 375 ° C 5 Minutes ~ 2 hours, and finally heated over 375 ° C ~ 450 ° C for 30 minutes ~ 4 hours.

Examples of the apparatus used for heating include a hot plate, an oven, and the like. The heating environment can be under air or under an inert gas, and under normal pressure or under reduced pressure.

In particular, when the thickness of the resin film is used as a substrate for a flexible display, it is usually about 1 to 60 μm, preferably about 5 to 50 μm, and the thickness of the coating film before heating is adjusted to form a resin film having a desired thickness.

The resin film described above is suitable for use as a base film of a flexible display substrate because it satisfies the required performance required as a base film of a flexible display substrate.

[Examples]

The following examples are given to illustrate the invention, but the invention is not limited by the following examples.

[1] The abbreviation used in the embodiment

<Acid anhydride>

PMDA: pyromellitic anhydride

4EPA: 4-ethynyl phthalic anhydride

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride

<amine>

PDA: p-phenylenediamine

FDA: 9,9-bis(4-aminophenyl)anthracene

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

4EA: 4-ethynylaniline

<solvent>

NMP: N-methyl-2-pyrrolidone

[2] Preparation of resin composition for display substrate (synthesis of poly-proline)

<Example 1>

0.446 g (0.0041 mol) of PDA, 0.187 g (0.00054 mol) of FDA and 0.198 g (0.00054 mol) of BAPB were dissolved in 23.0 g of NMP, and after adding 1.17 g (0.0054 mol) of PMDA, under nitrogen atmosphere, The reaction was carried out at 23 ° C for 24 hours. The obtained polymer had a Mw of 175,100 and a molecular weight distribution of 2.5. This solution was used as a resin composition for a display substrate.

Furthermore, the measurement of the weight molecular weight (Mw) and the molecular weight distribution is such that GPC apparatus manufactured by Japan Spectrophotometer (column: Shodex SB803HQ and SB804HQ; dissolution solvent: dimethylformamide; flow rate: 0.9 mL/min; column temperature: 40 ° C; Mw: polystyrene conversion value) Carry out (the same below).

<Example 2>

0.493 g (0.0046 mol) of PDA, 0.206 g (0.00059 mol) of FDA and 0.218 g (0.00059 mol) of BAPB were dissolved in 22.8 g of NMP, and after adding 1.29 g (0.0059 mol) of PMDA, under nitrogen atmosphere, After stirring at 23 ° C for 1 hour, 4EA 0.0416 g (0.00036 mol) was added and the reaction was further carried out for 23 hours. The obtained polymer had an Mw of 123,500 and a molecular weight distribution of 2.3. This solution was used as a resin composition for a display substrate.

<Example 3>

0.487 g (0.0045 mol) of PDA, 0.204 g (0.00058 mol) of FDA and 0.215 g (0.00058 mol) of BAPB were dissolved in 22.8 g of NMP, and after adding 1.28 g (0.0058 mol) of PMDA, under nitrogen atmosphere, After stirring at 23 ° C for 1 hour, 0.0685 g (0.00059 mol) of 4EA was added and further reacted for 23 hours. The obtained polymer had an Mw of 114,800 and a molecular weight distribution of 2.3. This solution was used as a resin composition for a display substrate.

<Example 4>

PDA 0.601g (0.0056 mol), FDA 0.258g (0.00074 mol) and BAPB 0.273g (0.00074 mol) were dissolved in N2.3 22.3g, PMDA 1.62g (0.0074 mol) was added, and under nitrogen environment, 23 ° C anti Should be 24 hours. The obtained polymer had a Mw of 147,800 and a molecular weight distribution of 2.5. This solution was used as a resin composition for a display substrate.

<Example 5>

PDA 0.636g (0.0059 mol), FDA 0.273g (0.00078 mol) and BAPB 0.289g (0.00078 mol) were dissolved in NMP 22.0g, and after adding 1.71g (0.0078 mol) of PMDA, under nitrogen environment, After stirring at 23 ° C for 1 hour, 4EA 0.0919 g (0.00078 mol) was added and the reaction was further carried out for 23 hours. The obtained polymer had an Mw of 128,700 and a molecular weight distribution of 2.4. This solution was used as a resin composition for a display substrate.

<Example 6>

0.578 g (0.0053 mol) of PDA, 0.233 g (0.00067 mol) of FDA and 0.246 g (0.00067 mol) of BAPB were dissolved in 22.5 g of NMP, and after adding 1.44 g (0.0066 mol) of PMDA, under nitrogen atmosphere, The reaction was carried out at 23 ° C for 24 hours. The obtained polymer had a Mw of 143,800 and a molecular weight distribution of 3.4. This solution was used as a resin composition for a display substrate.

<Example 7>

PDA 0.760g (0.0070 mol), FDA 0.306g (0.00089 mol) and BAPB 0.324g (0.00089 mol) were dissolved in NMP 21.8g, and after adding PMDA 1.86g (0.0085 mol), under nitrogen environment, The reaction was carried out at 23 ° C for 24 hours. The obtained polymer had an Mw of 65,300 and a molecular weight distribution of 3.1. This solution was used as a resin composition for a display substrate.

<Example 8>

PDA 0.601g (0.0056 mol), FDA 0.242g (0.00070 mol) and BAPB 0.256g (0.00070 mol) were dissolved in 22.4g of NMP, and after adding 1.50g (0.0069mol) of PMDA, under nitrogen environment, After stirring at 23 ° C for 1 hour, 4 239 0.0239 g (0.00014 mol) was added, and the reaction was further carried out for 23 hours. The obtained polymer had an Mw of 87,400 and a molecular weight distribution of 1.9. This solution was used as a resin composition for a display substrate.

<Example 9>

0.591 g (0.0055 mol), FDA 0.238 g (0.00068 mol) and BAPB 0.252 g (0.00068 mol) of PDA were dissolved in 22.4 g of NMP, and after adding 1.47 g (0.0068 mol) of PMDA, under nitrogen atmosphere, After stirring at 23 ° C for 1 hour, 4 EPA 0.0705 g (0.00041 mol) was added, and the reaction was further carried out for 23 hours. The obtained polymer had a Mw of 78,100 and a molecular weight distribution of 2.1. This solution was used as a resin composition for a display substrate.

<Example 10>

PDA 0.797g (0.0074 mole), FDA 0.321g (0.00092 mole) and BAPB 0.339g (0.00092 mole) were dissolved in NMP 21.5g, PMDA 1.95g (0.0089 moles) was added, under nitrogen environment, After stirring at 23 ° C for 1 hour, 4 EPA 0.0951 g (0.00055 mol) was added, and the reaction was further carried out for 23 hours. The obtained polymer had an Mw of 58,000 and a molecular weight distribution of 2.4. This solution was used as a resin composition for a display substrate.

<Comparative Example 1>

Add PDA 0.780g (0.0072 mol), FDA 0.314g (0.00090 mol) and BAPB 0.332g (0.00090 mol) to NMP 21.3g, add PMDA 0.865g (0.0040 mol) and BPDA 1.46g (0.0050 mo After the ear, it was reacted at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had an Mw of 81,900 and a molecular weight distribution of 3.3. This solution was used as a resin composition.

[3] Production of resin film for display substrate (production of polyimide film)

<Example 11>

The resin composition for a display substrate obtained in Example 1 was applied onto a glass substrate by a doctor blade at 120 ° C for 30 minutes, then at 150 ° C for 30 minutes, then at 180 ° C for 30 minutes. Baking in the air, followed by baking at 210 ° C, 30 minutes, followed by 240 ° C, 30 minutes, followed by 300 ° C, 20 minutes, then 400 ° C, 60 minutes, in a nitrogen atmosphere to make a resin film .

<Examples 12 to 20 and Comparative Example 2>

In the same manner as in Example 11, except that the resin composition for a display substrate obtained in Examples 2 to 10 and the resin composition obtained in Comparative Example 1 were used in place of the resin composition for a display substrate obtained in Example 1, respectively. Resin film.

[4] Evaluation of resin film

The evaluation of the obtained resin film was carried out by the following method. The results are shown in Table 1. Further, films for each evaluation were separately prepared. The film thickness is expressed by the value of the resin film used for the evaluation of the flexibility.

<Measurement of film thickness>

The film thickness of the resin film was measured using a micrometer made by Mitutoyo.

<heat resistance evaluation>

The 5% mass reduction temperature (Td 5% (° C.)) of the resin film was measured. The measurement was carried out using TG/DTA2000SA manufactured by Bruker AXS (stock) (heating rate: from 50 ° C to 800 ° C at 10 ° C per minute).

<Release and softness evaluation>

The ease of peeling when the resin film was peeled off from the glass substrate was evaluated. The peelability was evaluated by cutting a slit of a resin film formed on a glass substrate using a cutting blade, and confirming whether or not the strip-shaped film can be easily peeled off from the glass substrate. Since the blade is inserted between the film and the glass substrate, the film can be peeled off without being hooked, and it is not good.

Further, the flexibility of the peeled resin film was evaluated. The evaluation of the softness was carried out by visually confirming the ease of destruction (cracking, cracking, cracking, etc.) of the peeled resin film by hand bending or stretching. It is good if it is not broken even if it is bent or stretched by 90 degrees. The situation is bad.

<Measurement of linear expansion coefficient>

The linear expansion coefficient of the resin film was measured. The measurement was carried out using TMA-60 (heating rate: heating from 50 ° C to 400 ° C at 10 ° C per minute) manufactured by Shimadzu Corporation. Further, the coefficient is displayed as an average value of each temperature region on the low temperature (100 ° C to 250 ° C) side and the high temperature (250 ° C to 400 ° C) side.

As shown in Table 1, the heat resistance and flexibility of the resin film of Comparative Example 2 were the same as those of the resin film of the example, but the peeling property of the glass substrate was poor, and it was in a high temperature region (250 ° C to 400 ° C). The linear expansion coefficient is as high as 22 ppm. On the other hand, the resin films of Examples 11 to 20 have excellent peeling properties from the glass substrate, high heat resistance, and moderate flexibility, and have an appropriate linear expansion coefficient in any temperature region of low temperature and high temperature.

To use a resin film as a display substrate, it must be High heat resistance, moderate softness and moderate linear expansion coefficient.

In addition, in general, in the manufacture of a display, a resin film is applied by heating a resin composition on a substrate to form a resin film, and the resin film formed on the substrate is not peeled off, and an active matrix layer is sequentially formed thereon. Since the resin film is finally peeled off from the substrate, the resin film for a substrate preferably has good peelability from the substrate.

From the above results, it is understood that the resin film obtained from the resin composition of the present invention is particularly suitable for display substrate use because it has high heat resistance, moderate flexibility, and moderate linear expansion coefficient, and exhibits good peelability from the substrate. .

Claims (10)

A resin composition for a display substrate, comprising a polyglycine having a weight average molecular weight of 5,000 or more in three structural units represented by the formula (1-1) in a total of at least 50 mol%; Wherein Ar ¹ represents a divalent group represented by any one of the formulae (2) to (4), Ar ² represents a divalent group represented by the formula (5), and Ar ³ represents a divalent group represented by the formula (6) , Ar ⁴ represents a tetravalent group represented by the formula (7) or (8), and n ¹ to n ³ represent the number of each structural unit, and satisfy n ¹ /(n ² +n ³ )=2.0 to 9.0 and n ² / n ³ =0.1~10〕; The resin composition for a display substrate according to claim 1, wherein the polyamic acid is represented by the formula (1-2). In the formula (1-2), X ¹ represents a monovalent group represented by the formula (9) or (10), and X ² represents a monovalent group represented by the formula (11) or (12), and Ar ¹ to Ar ⁴ and n ¹ to n ³ represents the same meaning as described above, and X ₁ and X ₂ are independently bonded arbitrarily to the three structural units represented by the formula (1-1); [In the formulae (9) to (12), Y ¹ represents a divalent group represented by any one of the formulae (13) to (15), Y ² represents a monovalent group represented by the formula (16), and Ar ⁵ represents the above formula. (2) The divalent group represented by any one of (6), and Ar ⁴ represents a tetravalent group represented by the above formula (7) or (8); (In the formulae (13) to (16), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a monovalent group represented by the formula (17) or (18), q Represents the number of Z bonded to the benzene ring, and represents an integer from 1 to 3; (In the formulae (17) and (18), R ⁵ to R ⁸ each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms))]}. A resin film for a display substrate produced by using the resin composition for a display substrate according to claim 1 or claim 2. A resin film for a display substrate, which is coated on a substrate with a resin composition for a display substrate according to claim 1 or claim 2, and is heated at 50 ° C to 100 ° C for 5 minutes to 2 hours at a temperature exceeding 100 It is heated at °C~200°C for 5 minutes~2 hours, heated at over 200°C~375°C for 5 minutes~2 hours, and heated at over 375°C~450°C for 30 minutes~4 hours. An image display device comprising the resin film for a display substrate according to claim 3 or claim 4. A method for producing a resin film for a display substrate, which is characterized by using the resin composition for a display substrate according to claim 1 or claim 2. A method for producing a resin film for a display substrate, characterized in that the resin composition for a display substrate according to claim 1 or claim 2 is applied onto a substrate, and heated at 50 ° C to 100 ° C for 5 minutes to 2 seconds. After heating for more than 100 ° C ~ 200 ° C for 5 minutes to 2 hours, more than 200 ° C ~ 375 ° C for 5 minutes to 2 hours, more than 375 ° C ~ 450 ° C for 30 minutes to 4 hours. A method of manufacturing an image display device using the resin film for a display substrate according to claim 3 or claim 4. A polyaminic acid containing at least 50 mol% of the total of three structural units represented by the formula (1-1), and having a weight average molecular weight of 5,000 or more. Wherein Ar ¹ represents a divalent group represented by any one of the formulae (2) to (4), Ar ² represents a divalent group represented by the formula (5), and Ar ³ represents a divalent group represented by the formula (6) , Ar ⁴ represents a tetravalent group represented by the formula (7) or (8), and n ¹ to n ³ represent the number of each structural unit, and satisfy n ¹ /(n ² +n ³ )=2.0 to 9.0 and n ² / n ³ =0.1~10〕; The polyamic acid of claim 9, which is represented by formula (1-2), In the formula (1-2), X ¹ represents a monovalent group represented by the formula (9) or (10), and X ² represents a monovalent group represented by the formula (11) or (12), and Ar ¹ to Ar ⁴ and n ¹ to n ³ represents the same meaning as described above, and X ₁ and X ₂ are independently bonded arbitrarily to the three structural units represented by the formula (1-1); [In the formulae (9) to (12), Y ¹ represents a divalent group represented by any one of the formulae (13) to (15), Y ² represents a monovalent group represented by the formula (16), and Ar ⁵ represents the above formula. (2) The divalent group represented by any one of (6), and Ar ⁴ represents a tetravalent group represented by the formula (7) or the formula (8); (In the formulae (13) to (16), R ¹ to R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and Z represents a monovalent group represented by the formula (17) or (18), q Represents the number of Z bonded to the benzene ring, and represents an integer from 1 to 3; (In the formulae (17) and (18), R ⁵ to R ⁸ each independently represent a hydrogen atom or an aryl group having 6 to 20 carbon atoms))]}.