TWI610963B - Resin composition for display substrate - Google Patents

Abstract

An object of the present invention is to provide a resin composition for a display substrate which can form a useful polyimide film having an appropriate linear expansion coefficient and moderate flexibility.

The means for solving the problem is a resin composition for a display substrate, which comprises a polylysine or a polyimine which is a structural unit and a formula represented by the following formula (1) (3) In the structural unit shown, the polyimine is a structural unit represented by the following formula (2) and a structural unit represented by the formula (4). [in equations (1) to (4), X¹Shown as a tetravalent organic group having an aromatic group and two carbonyl groups, Y¹Shown as a divalent aromatic or aliphatic group, Y²It is shown as a divalent aromatic group having two or more nitrogen atoms, and n and m are shown as natural numbers.

Description

Resin composition for display substrate

The present invention relates to a resin composition for a display substrate, and more particularly to a resin composition for a display substrate, which is capable of forming a useful polyimide film having an appropriate linear expansion coefficient and moderate flexibility.

Polyimine resin, because of its high heat resistance, flame retardancy and electrical insulation, is therefore electrical. It is widely used in the field of electronic materials. Specifically, it is used for "a flexible printed wiring board as a film, a base material of a heat-resistant adhesive tape, an insulating film, a protective film, or the like of a semiconductor of a resin varnish."

On the other hand, display devices such as organic EL (Electroluminescence) displays and liquid crystal displays have only required high definition in the past, but this use is rapidly expanding in information devices and the like. For example, in order to meet the ultra-thin type. A lightweight display using a plastic film as a substrate has attracted attention as a result of weight reduction.

In the past, high-definition displays were panels that used active matrix drives. In addition to the matrix-shaped pixel electrode, when forming an active matrix layer including a thin film active device, the manufacturing process must be performed at a high temperature of 200 ° C or higher, and must be an extremely correct alignment. However, since it is flexible, it changes from a glass substrate to a plastic material. However, since heat resistance and dimensional stability are poor, it is extremely difficult to form an active element directly on a plastic material.

Here, in order to avoid the problems as described above, it has been proposed as follows Method: "The polyimide film is formed on a glass substrate, and the production conditions are not limited. The amorphous germanium TFT element or the color filter is aligned and formed at a high fineness to form a transfer layer, and then borrowed. A method of producing a display element by transferring the transfer layer onto a plastic film (Patent Documents 1 and 2).

However, as a characteristic of the polyimine which is necessary in the foregoing steps, for example, a linear expansion coefficient is exemplified. However, for most polyimine systems, the linear expansion coefficient of the film is in the range of 60 to 80 ppm/K, and does not have low linear expansion characteristics. Among these, although a polyimine film having a low coefficient of linear expansion has been developed, the use of an acid dianhydride which is lacking in general use as a raw material has resulted in a high price (Patent Document 3).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-356370

[Patent Document 2] Japanese Patent Publication No. 2010-539293

[Patent Document 3] International Publication No. 2008/047591

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a resin composition for a display substrate which can form a moderate linear expansion coefficient and moderate flexibility without using a general-purpose acid dianhydride. A useful hardened film with sufficient heat resistance. Still, the so-called moderate The softness is self-supporting and refers to a high degree of softness which does not break even if it is bent at 90 degrees.

In order to achieve the above object, the inventors of the present invention have conducted intensive studies and found that a resin composition for a display substrate is obtained by combining an acid anhydride having a biphenyl skeleton as an acid dianhydride component and a benzoic acid as a diamine component. The diamine of imidazole is used, and comprises polyamic acid or polyimine derived from the acid dianhydride component and the diamine component, and a resin composition of the display substrate can have a moderate linear expansion coefficient. The present invention has been completed by a useful hardened film of moderate flexibility.

〔式(1)至式(4)中，X¹示為具有芳香族基與2個羰基之四價之有機基，Y¹示為二價之芳香族基或脂肪族基，Y²示為具有2個以上氮原子之二價之芳香族基，n及m示為自然數〕。 In a first aspect of the present invention, a resin composition for a display substrate comprising the following polyacrylic acid or a polyimine containing the following formula (1) In the structural unit and the structural unit represented by the formula (3), the polyimine is a structural unit represented by the following formula (2) and a structural unit represented by the formula (4).

[Formula (1) to (4), X ¹ is shown as having a tetravalent aromatic group and the two carbonyl groups of an organic group, Y ¹ is a diagram of a divalent aromatic group or aliphatic group, Y ² is shown A divalent aromatic group having two or more nitrogen atoms, n and m are shown as natural numbers.

. The second aspect is the resin composition for a display substrate according to the first aspect, wherein the Y ² is an aromatic group having a heterocyclic structure.

(式中，R¹至R⁷分別獨立示為氫原子、碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基、羧基、可被 W¹取代之苯基、可被W¹取代之萘基、可被W¹取代之噻吩基或可被W¹取代之呋喃基，W¹示為碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基或羧基，A示為氫原子、碳原子數1至10之烷基或碳原子數1至10之鹵烷基，尚，○示為鍵結鍵)。 . The third aspect is the resin composition for a display substrate according to the second aspect, wherein the Y ² is represented by the following formula (5).

(wherein R ¹ to R ⁷ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. A group or a carboxyl group, A is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and ○ is a bond.

. As a fourth aspect is a display board with respect to the third aspect of the resin composition, wherein the R ¹ to R ⁷ and A is a hydrogen atom shown.

(式中，R⁸至R¹¹分別獨立示為氫原子、碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基、羧基、可被W¹取代之苯基、可被W¹取代之萘基、可被W¹取代之噻吩基或可被W¹取代之呋喃基，W¹示為碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基或羧基，q示為1或2，尚，○示為鍵結鍵)。 . The resin composition for a display substrate according to any one of the first to fourth aspects, wherein the Y ¹ is represented by the following formula (6),

(wherein R ⁸ to R ¹¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Base or carboxyl group, q is shown as 1 or 2, and ○ is shown as a bond.

. According to a sixth aspect of the invention, the resin composition for a display substrate according to the fifth aspect, wherein the divalent aromatic group represented by the formula (6) is derived from phenylenediamine.

. The seventh aspect of the invention is the resin composition for a display substrate according to the sixth aspect, wherein the R ⁸ to R ¹¹ are a hydrogen atom.

(式中，R¹²至R²¹分別獨立示為氫原子、碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基、羧基、可被W¹取代之苯基、可被W¹取代之萘基、可被W¹取代之噻吩基或可被W¹取代之呋喃基，W¹示為碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基或羧基，Z¹及Z²分別獨立示為-NH-、-NZ³-或氧原子，Z³示為碳原子數1至10之烷基，p示為1或2，尚，○示為鍵結鍵)。 . The resin composition for a display substrate according to any one of the first to seventh aspects, wherein the X ¹ is represented by the following formula (7),

(wherein R ¹² to R ²¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Or a carboxyl group, Z ¹ and Z ² are each independently shown as -NH-, -NZ ³ - or an oxygen atom, Z ^{3 is} shown as an alkyl group having 1 to 10 carbon atoms, p is 1 or 2, still, ○ For the keying button).

. The ninth aspect is the resin composition for a display substrate according to the eighth aspect, wherein the p is 2 .

. A tenth aspect is the ninth aspect on the display substrate with the resin composition, wherein the foregoing R ¹² to R ²¹ is a hydrogen atom shown.

. The resin composition for a display substrate according to any one of the first to tenth aspects, wherein n in the above formula (1) and m in the above formula (3) are n/m = 70/30 to 99/1 relationship.

. The resin composition for a display substrate according to any one of the first to tenth aspects, wherein n in the above formula (2) and m in the above formula (4) are n/m = 70/30 to 99/1 relationship.

. The resin composition for a display substrate according to any one of the first to twelfth aspects, further comprising a crosslinking agent.

. The resin composition for a display substrate according to the thirteenth aspect, wherein the crosslinking agent is a compound having two or more epoxy groups.

. The resin composition for a display substrate according to the fourteenth aspect, wherein the crosslinking agent is a compound having an aromatic group.

. The resin composition for a display substrate according to the fifteenth aspect, wherein the crosslinking agent is a compound having 6 or less epoxy groups, and the compound is a carbon atom having a bonding epoxy group and an aromatic group. A number of from 1 to 10 alkyl groups.

. The resin composition for a display substrate according to any one of the above aspects of the present invention, wherein the crosslinking agent is 20 parts by mass or less based on 100 parts by mass of the polyamic acid or polyimine.

. The 18th point is about a varnish, which is in the first to the 17th viewpoints. The resin composition for a display substrate of any one of them is dissolved in at least one solvent.

. The ninth aspect relates to a cured film obtained by calcining at a temperature of 230 degrees or more using the varnish of the eighteenth aspect.

. The twentieth aspect is a structure in which at least one layer of the cured film of the 19th aspect is provided on the substrate.

〔式(1)及式(3)中，X¹示為具有芳香族基與2個羰基之四價之有機基，Y¹示為二價之芳香族基或脂肪族基，Y²示為具有2個以上氮原子之二價之芳香族基，n及m示為自然數〕。 . The twenty-first aspect relates to a polylysine comprising a structural unit represented by the following formula (1) and a structural unit represented by the formula (3).

[In the formulae (1) and (3), X ¹ is a tetravalent organic group having an aromatic group and two carbonyl groups, and Y ¹ is a divalent aromatic group or an aliphatic group, and Y ² is represented by A divalent aromatic group having two or more nitrogen atoms, n and m are shown as natural numbers.

〔式(2)及式(4)中，X¹示為具有芳香族基與2個羰基之四價之有機基，Y¹示為二價之芳香族基或脂肪族基，Y²示為具有2個以上氮原子之二價之芳香族基，n及m示為自然數〕。 . The 22nd aspect relates to a polyimine which comprises a structural unit represented by the following formula (2) and a structural unit represented by the formula (4),

[In the formulae (2) and (4), X ¹ is a tetravalent organic group having an aromatic group and two carbonyl groups, and Y ¹ is a divalent aromatic group or an aliphatic group, and Y ² is represented by A divalent aromatic group having two or more nitrogen atoms, n and m are shown as natural numbers.

. The twenty-third aspect is a substrate for a display formed of the polyimine of the twenty-second aspect.

The resin composition for a display substrate of the present invention can form a useful cured film having an appropriate linear expansion coefficient, moderate flexibility, and sufficient heat resistance. Therefore, the cured film can be used for a base film or the like for a flexible display.

[Best Mode for Carrying Out the Invention] [Resin composition for display substrate]

The present invention relates to a resin composition for a display substrate, which comprises: "a polyamic acid comprising a structural unit represented by the following formula (1) and a structural unit represented by the formula (3)" or "including the following formula" (2) The structural unit and formula (4) The structural unit of the polyimine shown.

〔式(1)至式(4)中，X¹示為具有芳香族基與2個羰基之四價之有機基，Y¹示為二價之芳香族基或脂肪族基，Y²示為具有2個以上氮原子之二價之芳香族基，n及m示為自然數〕。

[In the formulae (1) to (4), X ¹ is a tetravalent organic group having an aromatic group and two carbonyl groups, and Y ¹ is a divalent aromatic group or an aliphatic group, and Y ² is represented by A divalent aromatic group having two or more nitrogen atoms, n and m are shown as natural numbers.

Here, the above-mentioned polyamic acid containing the structural unit represented by the formula (1) and the structural unit represented by the formula (3) means that n structural units represented by the following formula (a) and m are as follows. a structural unit represented by the formula (b), and the (n+m) structural units are compounds bonded in an arbitrary order; the above-mentioned so-called structural unit represented by the formula (2) and the formula (4) The polyimine of the structural unit means that n structural units represented by the following formula (c) and m structural units represented by the following formula (d) are contained, and the structural units of (n+m) are Compounds bonded in any order.

Further, the polyamic acid containing the structural unit represented by the formula (1) and the structural unit represented by the formula (3) may have a structure represented by the following formula (c) in the molecule. And either or both of the structural units represented by the formula (d); and the polyimine containing the structural unit represented by the formula (2) and the structural unit represented by the formula (4), may have the following in the molecule Either or both of the structural unit represented by the formula (a) and the structural unit represented by the formula (b).

〔式(a)至式(d)中，X¹、Y¹及Y²分別與前述式(1)至式(4)中之定義示為同義〕。

[In the formulae (a) to (d), X ¹ , Y ¹ and Y ² are each shown to be synonymous with the definitions in the above formulas (1) to (4)].

In the resin composition for a display substrate, the content of the polyamic acid or polyamidiamine (polyuric acid and polyimine if both are contained) is based on the content of the solid content of the resin composition. 8 to 99.9% by mass, preferably 40 to 99.9% by mass, more preferably 80 to 99.9% by mass.

Here, the solid content refers to a residual component obtained by removing a solvent from the total components of the resin composition for a display substrate.

The resin composition for a display substrate of the present invention contains polyamic acid or polyimine.

<polylysine>

The polylysine contained in the resin composition for a display substrate of the present invention can be obtained by polymerizing an acid anhydride component and a diamine component in a solvent.

(式中，X¹示為具有芳香族基與2個以上羰基之四價之有機基)所示的至少1種之酸二酐，與下述式(9)：H₂N-Y¹-NH₂ (9)(式中，Y¹示為二價之芳香族基或脂肪族基)所示的至少1種之二胺，與下述式(10)：H₂N-Y²-NH₂ (10)(式中，Y²示為具有2個以上氮原子之二價之芳香族基)所示的至少1種之二胺，於溶劑中溶解、反應而得到。 Polylysine can be obtained by a conventional method, for example, in an inert gas atmosphere such as nitrogen, to give the following formula (8):

(wherein X ¹ is an acid dianhydride represented by an aromatic group and a tetravalent organic group of two or more carbonyl groups), and the following formula (9): H ₂ NY ¹ -NH ₂ (9) (in the formula, Y ¹ is a divalent aromatic group or an aliphatic group), and at least one diamine represented by the following formula (10): H ₂ NY ² -NH ₂ (10) (In the formula, Y ² is a diamine represented by a divalent aromatic group having two or more nitrogen atoms), which is obtained by dissolving and reacting in a solvent.

The reaction temperature at this time is -20 to 100 ° C, preferably 20 to 60 ° C. The reaction time is from 1 to 72 hours.

In the present invention, the reaction solution of poly-proline can be directly or diluted Alternatively, the polyamic acid recovered from the reaction solution by reprecipitation or the like is redissolved or dispersed in a suitable solvent to be used as a resin composition for a display substrate. The solvent to be used for the dilution, re-dissolution or dispersion is not particularly limited as long as it can dissolve or disperse the obtained poly-proline, and examples thereof include 2-pyrrolidone and N-methyl-2-pyrrolidone. N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3-methoxy- N,N-Dimethylpropyl decylamine, 3-ethoxy-N,N-dimethylpropyl decylamine, 3-propoxy-N,N-dimethylpropyl decylamine, 3- Isopropoxy-N,N-dimethylpropyl decylamine, 3-butoxy-N,N-dimethylpropyl decylamine, 3-sec-butoxy-N,N-dimethyl Propylguanamine, 3-tert-butoxy-N,N-dimethylpropylguanamine, γ-butyrolactone, and the like. These solvents may be used alone or in combination of two or more.

As the acid dianhydride represented by the above formula (8), X ^{1 is} preferably an acid dianhydride having a structure represented by the following formula (7), and X ^{1 is} particularly preferably an acid having a structure represented by the following formula (7-1). Diacid anhydride.

(式中， R¹²至R²¹分別獨立示為氫原子、碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基、羧基、可被W¹取代之苯基、可被W¹取代之萘基、可被W¹取代之噻吩基或可被W¹取代之呋喃基，W¹示為碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基或羧基，Z¹及Z²分別獨立示為-NH-、-NZ³-或氧原子，Z³示為碳原子數1至10之烷基，p示為1或2，尚，○示為鍵結鍵)。

(wherein R ¹² to R ²¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Or a carboxyl group, Z ¹ and Z ² are each independently shown as -NH-, -NZ ³ - or an oxygen atom, Z ^{3 is} shown as an alkyl group having 1 to 10 carbon atoms, p is 1 or 2, still, ○ For the keying button).

In the above formula (7), the above p is preferably 2.

As the acid dianhydride represented by the formula (8), for example, p-phenylenebis (trimellitic acid monoester anhydride), 2-methyl-1 is exemplified. , 4-phenylene bis(trimellitic acid monoester anhydride), 2,5-dimethyl-1,4-phenylene bis(trimellitic acid monoester anhydride), 2,3,5,6 - tetramethyl-1,4-phenylene bis(trimellitic acid monoester anhydride), 2-trifluoromethyl-1,4-phenylene bis(trimellitic acid monoester anhydride), 2, 5-bis(trifluoromethyl)-1,4-phenylene bis(p-trimellitic acid monoester anhydride), 2-chloro-1,4-phenylene bis(trimellitic acid monoester anhydride), 2,5-Dichloro-1,4-phenylene bis(trimellitic acid monoester anhydride), 2-fluoro-1,4-phenylene bis(trimellitic acid monoester anhydride) and 2,5 -difluoro-1,4-phenylene bis(trimellitic acid monoester anhydride), and N,N'-(1,4-phenylene)bis(1,3-dioxo-1,3) -dihydrobenzofuran-5-carboxyguanamine) and N,N'-(1,4-phenylene)bis(N-methyl- 1,3-dioxo-1,3-dihydrobenzofuran-5-carboxyguanamine) and the like.

Among the acid dianhydrides, the cured film obtained by the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength. R ¹² to the above formula (7) is preferred. R ²¹ is a hydrogen atom, Z ¹ and Z ^{2 are} shown as oxygen atoms, and p is a compound of 2, 4,4′-biphenyl bis(trimellitic acid monoester anhydride) (the following formula (11)) .

The aromatic or aliphatic diamine represented by the above formula (9) is preferably a rigid line obtained from the viewpoint that the cured film obtained by the resin composition of the present invention has a sufficiently low coefficient of linear expansion. A diamine of molecular structure. In the diamine represented by the above formula (9), Y ^{1 is} preferably a diamine having a structure represented by the following formula (6), and Y ^{1 is} particularly preferably a structure represented by the following formula (6-1). Diamine.

(式中，R⁸至R¹¹分別獨立示為氫原子、碳原子數1至10之 烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基、羧基、可被W¹取代之苯基、可被W¹取代之萘基、可被W¹取代之噻吩基或可被W¹取代之呋喃基，W¹示為碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基或羧基，q示為1或2，尚，○示為鍵結鍵)。

(wherein R ⁸ to R ¹¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Base or carboxyl group, q is shown as 1 or 2, and ○ is shown as a bond.

The divalent aromatic group represented by the above formula (6) is preferably one derived from phenylenediamine.

Further, in the above formula (6), the above-mentioned R ⁸ to R ^{11 are} preferably a hydrogen atom from the viewpoint that the cured film obtained by the resin composition of the present invention has a sufficiently low linear expansion coefficient and a sufficiently high strength. .

Examples of the aromatic diamine represented by the above formula (9) include p-phenylenediamine, o-phenylenediamine, methyl-1,4-phenylenediamine, and 2-trifluoromethyl-1,4-. Phenylenediamine, 2-methoxy-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,5-bis(trifluoromethyl)-1,4- Phenylenediamine, 4,4'-diaminobenzimidamide, 4-aminophenyl-4'-aminobenzoate, benzidine, 3,3'-dimethoxybenzidine, 3,3'-dichlorobenzidine, o-tolidine, m-tolidine, 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl) linkage Aniline, octafluorobenzidine, 3,3',5,5'-tetramethylbenzidine, 2,2',5,5'-tetrachlorobenzidine, etc., among these, the resin of the present invention The cured film obtained from the composition is preferably p-phenylenediamine and m-phenylenediamine from the viewpoint of having a sufficiently low linear expansion coefficient and a sufficiently high strength.

Examples of the aliphatic diamine represented by the above formula (9) include, for example, 4,4′-methylenebis(cyclohexylamine) and 4,4′-methylenebis(3-methylcyclohexylamine). Isophorone diamine, trans-1,4-cyclohexanediamine, cis-1,4-cyclohexanediamine, 1,4-cyclohexane bis(methylamine), 2,5-bis (amine) Methyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 3,8-bis(aminomethyl)tricyclo[5.2.1.0癸 decane, 1,3-diamine adamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-aminocyclohexyl)hexafluoropropane, 1,3- Propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1, 8-octamethyldiamine, 1,9-nonamethylenediamine, and the like.

Among the above aliphatic diamines, it is preferred to use a diamine having a rigid linear molecular structure from the viewpoint that the cured film obtained by the resin composition of the present invention has a sufficiently low linear expansion coefficient. For example, trans-1,4-cyclohexanediamine is used.

Further, in the diamine represented by the above formula (10), it is preferred to use a rigid linear structure having a hardened film obtained by the resin composition of the present invention having a sufficiently low coefficient of linear expansion. Diamine.

唑、噻唑、四氮雜芘、咪唑吡咯酮(imidazopyrrolone)、喹

啉、吲哚喹

啉、異吲哚喹唑啉二酮等雜環結構之芳香族基之二胺；更佳為具有該雜環結構苯、萘、蒽等之芳香族環結構之芳香族基之二胺；較佳Y²為下述式(5)所示結構之二胺，特佳為Y²為下述式(5-1)所示結構之二胺。 Among them, as the diamine represented by the above formula (10), it is preferred that Y ² has an imidazole.

Oxazole, thiazole, tetraazaindene, imidazopyrrolone, quinolin

Porphyrin

a diamine of an aromatic group having a heterocyclic structure such as a porphyrin or an isoindole quinazolinedione; more preferably a diamine having an aromatic ring structure of an aromatic ring structure such as benzene, naphthalene or anthracene; Jia Y ² is a diamine of the following formula (5) shown in structures, particularly preferably Y ² is a diamine of the following formula (5-1) structure FIG.

(式中，R¹至R⁷分別獨立示為氫原子、碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基、羧基、可被W¹取代之苯基、可被W¹取代之萘基、可被W¹取代之噻吩基或可被W¹取代之呋喃基，W¹示為碳原子數1至10之烷基、碳原子數1至10之鹵烷基、碳原子數1至10之烷氧基、羥基、鹵原子、硝基、甲醯基、氰基或羧基，A示為氫原子、碳原子數1至10之烷基或碳原子數1至10之鹵烷基，尚，○示為鍵結鍵)。

(wherein R ¹ to R ⁷ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. A group or a carboxyl group, A is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and ○ is a bond.

唑、2-(3-胺基苯基)-5-胺基苯并

唑、2-(4-胺基苯基)-5-胺基苯并咪唑、2-(3-胺基苯基)-5-胺基苯并咪唑、2-(4-胺基苯基)-5-胺基苯并噻唑、2-(3-胺基苯基)-5-胺基苯并二唑等。 As the diamine represented by the above formula (10), for example, 2-(4-aminophenyl)-5-aminobenzobenzene

Oxazole, 2-(3-aminophenyl)-5-aminobenzo

Oxazole, 2-(4-aminophenyl)-5-aminobenzimidazole, 2-(3-aminophenyl)-5-aminobenzimidazole, 2-(4-aminophenyl) 5-aminobenzothiazole, 2-(3-aminophenyl)-5-aminobenzoxazole, and the like.

Among the above diamines, from the viewpoints of easiness of obtaining and improving the self-supporting property of the cured film obtained by the resin composition of the present invention, R ¹ to R ⁷ and A in the above formula (5) are preferably 2-(3-Aminophenyl)-5-aminobenzimidazole of a compound of a hydrogen atom.

The solvent used in the formation reaction of polyproline is not particularly limited For example, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N-methylpyrrolidone, 3-methoxy -N,N-dimethylpropyl decylamine, 3-ethoxy-N,N-dimethylpropyl decylamine, 3-propoxy-N,N-dimethylpropyl decylamine, 3 -isopropoxy-N,N-dimethylpropyl decylamine, 3-butoxy-N,N-dimethylpropyl decylamine, 3-sec-butoxy-N,N-dimethyl Propyl decylamine, 3-tert-butoxy-N,N-dimethylpropyl decylamine, hexamethylphosphoniumamine, dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl Benzyl-2-imidazolidinone, 1,2-dimethoxyethane-bis(2-methoxyethyl)ether, tetrahydrofuran, 1,4-dioxane, methylpyridine, pyridine, acetone, chloroform, An aprotic solvent such as toluene or xylene; and a protic solvent such as phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol or p-chlorophenol. These solvents may be used alone or in combination of two or more.

The ratio of the diamine component in the above reaction is preferably from 70/30 to 99/1 in terms of the molar ratio of the diamine represented by the above formula (9) to the diamine represented by the above formula (10). The cured film obtained from the resin composition of the invention has a sufficiently low linear expansion coefficient and a sufficiently high strength, and more preferably from 75/25 to 95/5.

Further, the ratio of the acid dianhydride component to the diamine component in the above reaction is preferably an acid dianhydride component/diamine component = 0.8 to 1.2 in terms of a molar ratio. As with the general polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polymer formed. When the degree of polymerization is too small, the strength of the polyimide film of the polyimide may be insufficient, and when the degree of polymerization is too large, the workability at the time of forming the polyimide film of the polyimide may be deteriorated.

The weight average molecular weight of the produced polylysine, in order to The cured film obtained by the resin composition for a lysine display substrate has a strength of 3,000 to 200,000 in terms of polystyrene. When the weight average molecular weight is less than 3,000, the finished film has a possibility of becoming brittle; on the other hand, when the weight average molecular weight exceeds 200,000, the viscosity of the lysine of the polyaminic acid becomes high, and the result is changed. It is difficult to operate.

Among the polylysines produced, the relationship between the number n of the structural units represented by the formula (1) and the number m of the structural units represented by the formula (3) is preferably n/m = 70/30 to 99/1, more Good for 75/25 to 95/5.

In addition, in the case where the cured film obtained has a sufficiently low linear expansion coefficient and a sufficiently high strength, the repeating unit of the produced polylysine has a structure represented by the following formula (1-1). The ratio of the unit to the structural unit represented by the following formula (3-1) is preferably 70 mol% or more, more preferably 80 mol% or more, and still more preferably 85 mol% or more, in total of both; The structural unit represented by the following formula (1-1) is: "In the structural unit represented by the formula (1), X ¹ is a formula wherein R ¹² to R ²¹ are a hydrogen atom and Z ¹ and Z ² are oxygen atoms (7) The structure shown, and Y ¹ is a structure represented by the formula (6) in which R ⁸ to R ¹¹ are a hydrogen atom; the structural unit represented by the following formula (3-1) is: "the structure represented by the formula (3) In the unit, X ¹ is a structure represented by the formula (7) wherein R ¹² to R ²¹ are a hydrogen atom and Z ¹ and Z ² are an oxygen atom, and Y ² is a formula wherein R ¹ to R ⁷ and A are a hydrogen atom (5) ) the structure shown."

〔式中，q及p分別與前述式(6)及式(7)中之定義示為同義〕。

[wherein, q and p are respectively synonymous with the definitions in the above formulas (6) and (7)].

When the resin composition for a display substrate is produced by using the polyamic acid obtained by the method described above, in particular, when the resin composition is prepared by dissolving or dispersing in a solvent in the form of a varnish, it is preferable to include the following structure. In the structural unit represented by the formula (1), X ¹ is a structure represented by the following formula (7-2) and Y ¹ is a following formula (6-2). In the structure shown in the formula (3), X ¹ is a structure represented by the following formula (7-2) and Y ² is a structure represented by the following formula (5-2); In the structural unit represented by the formula (1), X ¹ is a structure represented by the following formula (7-3) and Y ¹ is as follows: In the structure represented by the formula (6-3), and in the structural unit represented by the formula (3), X ¹ is a structure represented by the following formula (7-3) and Y ² is a structure represented by the following formula (5-3). Further, it is more preferably a polyaminic acid (hereinafter referred to as a constitution C) containing the following structural unit: "In the structural unit represented by the formula (1), X ¹ is a formula of the formula of (p) 2 (7-3) ) and Y ¹ is a structure shown in the following formula and q is (the structure shown in 6-3) 1, and the formula (3) shown in the structural unit, X ¹ is of p is 2 Structure shown in the above formula (7-3), and Y ² is the following formula (5-3) shown by the structure. "

〔式中，q及p分別與前述式(6)及式(7)中之定義示為同義。尚，○示為鍵結鍵〕。

[wherein, q and p are respectively shown synonymous with the definitions in the above formulas (6) and (7). Still, ○ is shown as a bonding key].

More preferably, it is a polylysine as described below: "The composition of the formula (1) is the number n and the structure represented by the formula (3) under the preferred constitutions (constituting A, B or C). The number of units m is such that the relationship of n/m = 70/30 to 99/1 is satisfied, preferably the relationship of n/m = 75/25 to 95/5 is satisfied, and in the repeating unit of poly-proline, the above The ratio of the structural unit represented by the formula (1-1) to the structural unit represented by the above formula (3-1) is 70 mol% or more, preferably 80 mol% or more, and more preferably 85 mol. More than %, and the weight average molecular weight of polyamic acid is 3,000 to 200,000 (in terms of polystyrene).

Further, the above-mentioned "polyamic acid containing a structural unit represented by the formula (1) and a structural unit represented by the formula (3)" is also an object of the present invention.

<polyimine]

Polyaluminum contained in the resin composition for a display substrate of the present invention The amine can be obtained by subjecting the polylysine synthesized as described above to dehydration ring closure by heating (thermal oxime imidization). Further, in this case, the polyaminic acid may be converted into a quinone imine in a solvent, and then used as a solvent-soluble polyimine. Further, a chemical ring closure method using a conventional dehydration ring-closing catalyst can also be employed. The heating can be carried out at any temperature of from 100 to 300 ° C, preferably from 120 to 250 ° C. The chemical ring closure method can be carried out, for example, in the presence of pyridine or triethylamine with acetic anhydride or the like, and the temperature can be selected from any temperature of from -20 to 200 °C.

In the present invention, the reaction solution of the polyimine may be directly or diluted or concentrated, or the polyimine recovered by the reaction solution by reprecipitation or the like may be redissolved or dispersed in a suitable solvent. The display substrate is used as a resin composition. The solvent to be used for the dilution, re-dissolution or dispersion is not particularly limited as long as the obtained polyimine is dissolved or dispersed, and examples thereof include m-cresol, 2-pyrrolidone, and N-methyl-2. - pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, 3 -methoxy-N,N-dimethylpropyl decylamine, 3-ethoxy-N,N-dimethylpropyl decylamine, 3-propoxy-N,N-dimethylpropyl Indoleamine, 3-isopropoxy-N,N-dimethylpropylguanamine, 3-butoxy-N,N-dimethylpropylguanamine, 3-sec-butoxy-N, N-dimethylpropyl decylamine, 3-tert-butoxy-N,N-dimethylpropyl decylamine, γ-butyrolactone, and the like. These solvents may be used alone or in combination of two or more.

The weight average molecular weight of the produced polyimine is preferably 3,000 to 200,000 in terms of polystyrene in order to maintain the strength of the cured film obtained from the resin composition for a display substrate containing polyimide. When the weight is average When the molecular weight is less than 3,000, the completed film may be brittle; on the other hand, when the weight average molecular weight exceeds 200,000, the viscosity of the varnish of the polyimide may become high, and as a result, it becomes difficult to handle. .

In the polyimine formed, the relationship between the number n of the structural units represented by the formula (2) and the number m of the structural units represented by the formula (4) is preferably n/m = 70/30 to 99/1, more Good for 75/25 to 95/5.

In addition, in the case where the cured film obtained has a sufficiently low linear expansion coefficient and a sufficiently high strength, the repeating unit of the produced polyimine has a structure represented by the following formula (2-1). The ratio of the unit to the structural unit represented by the following formula (4-1) is preferably 70% by mole or more, more preferably 80% by mole or more, and still more preferably 85% by mole or more, based on the total of both parties; The structural unit represented by the following formula (2-1) is: "In the structural unit represented by the formula (2), X ¹ is a formula wherein R ¹² to R ²¹ are a hydrogen atom and Z ¹ and Z ² are an oxygen atom (7) The structure shown, and Y ¹ is a structure represented by the formula (6) in which R ⁸ to R ¹¹ are a hydrogen atom; the structural unit represented by the following formula (4-1) is: "the structure represented by the formula (4) In the unit, X ¹ is a structure represented by the formula (7) wherein R ¹² to R ²¹ are a hydrogen atom and Z ¹ and Z ² are an oxygen atom, and Y ² is a formula wherein R ¹ to R ⁷ and A are a hydrogen atom (5) ) the structure shown."

〔式中，q及p分別與前述式(6)及式(7)中之定義示為同義〕。

[wherein, q and p are respectively synonymous with the definitions in the above formulas (6) and (7)].

When the resin composition for a display substrate is produced by using the polyimine obtained by the method described above, in particular, when the resin composition is prepared by dissolving or dispersing in a solvent in the form of a varnish, it is preferable to include the following structure. In the structural unit represented by the formula (2), X ¹ is a structure represented by the above formula (7-2) and Y ¹ is a compound of the above formula (6-2). In the structure shown in the formula (4), X ¹ is a structure represented by the above formula (7-2) and Y ² is a structure represented by the above formula (5-2); more preferably, the following In the structural unit represented by the formula (2), X ¹ is a structure represented by the above formula (7-3) and Y ¹ is the above formula (6-3). In the structure shown, in the structural unit represented by the formula (4), X ¹ is a structure represented by the above formula (7-3) and Y ² is a structure represented by the above formula (5-3); more preferably, polyimide of the following structural unit (hereinafter referred to as configuration F): "formula (2) shown in structural unit, X ¹ and p is as shown in FIG. 2 of the above formula (7-3) and Y ¹ is the structure of q 1 of the above formula (6-3) structure of formula (4) shown in the structural unit, X ¹ is of p is 2 Structure shown in the above formula (7-3), and Y ² is the formula (5-3) shown by the structure. "

More preferably, it is preferably a polyimine such as the following: "In the preferred compositions (constituting D, E or F), the number of structural units represented by the formula (2) and the structure represented by the formula (4) The number of units m is such that the relationship of n/m = 70/30 to 99/1 is satisfied, preferably the relationship of n/m = 75/25 to 95/5 is satisfied, and in the repeating unit of polyimine, the above The ratio of the structural unit represented by the formula (2-1) to the structural unit represented by the above formula (4-1) is 70 mol% or more, preferably 80 mol% or more, and more preferably 85 mol. More than %, and the weight average molecular weight of the polyimine is 3,000 to 200,000 (in terms of polystyrene).

Further, the above-mentioned "polyimine comprising a structural unit represented by the formula (2) and a structural unit represented by the formula (4)" is also an object of the present invention.

The resin composition for a display substrate of the present invention may further comprise a polyamic acid comprising the structural unit represented by the formula (1) and a structural unit represented by the formula (3), and the structural unit and the formula represented by the above formula (2). (4) Both of the structural units of the polyimine.

The resin composition for a display substrate of the present invention preferably contains a solvent, and the polyaminic acid or polyimine is dissolved or uniformly dispersed; more preferably, the polyamic acid or the polyimine is dissolved in a solvent. By. As such a solvent, for example, a solvent used in the formation reaction of the above polyamic acid is exemplified.

Moreover, the resin composition for a display substrate of the present invention may contain a crosslinking agent (hereinafter also referred to as a crosslinkable compound).

<crosslinker>

環為具有平均3個以上未滿6個之羥甲基或烷氧基甲基者。 The crosslinkable compound has at least one of polyacrylic acid and polyamidiamine in the step of converting a coating film (which is obtained by using the positive photosensitive resin composition) into a cured film. The compound to be subjected to the organic group reaction is not particularly limited. Examples of such a compound include a compound containing two or more epoxy groups, or a melamine derivative having a hydrogen atom of an amine group, which is substituted by a methylol group, an alkoxymethyl group or both thereof, and benzoquinone. A benzoguanamine derivative or a glycoluril or the like. The melamine derivative and the benzoguanamine derivative may be a dimer or a trimer, and may be a mixture selected from the group consisting of a monolith, a dimer and a trimer. These melamine derivatives and benzoguanamine derivatives are preferably each one of three

The ring is one having an average of 3 or more and less than 6 hydroxymethyl groups or alkoxymethyl groups.

Further, the crosslinking agents used in the present invention may be used alone or in combination of two or more.

Specific examples of the crosslinkable compound are exemplified 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, Celoxide 2021, and Celoxide 3000 (above, DAICEL Chemical Industry Co., Ltd.). Epoxy compound having a cyclohexene structure; bisphenol A type ring such as Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above, Japan Epoxy Resin) Oxygen compound; bisphenol F type such as Epikote 807 (made by Japan Epoxy Resin Co., Ltd.) Epoxy epoxide type epoxy compound such as Epikote 152, Epikote 154 (above: Japan Epoxy Resin Co., Ltd.), EPPN 201, EPPN 202 (above: Nippon Chemical Co., Ltd.); ECON-102, ECON a cresol novolac type epoxy compound such as -103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (the above is manufactured by Nippon Kayaku Co., Ltd.), and Epikote 180S75 (made by Japan Epoxy Resin Co., Ltd.); Naphthalene type epoxy compound such as V8000-C7 (made by DIC); Denacol EX-252 (manufactured by Nagasechemtex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 ( The above is made by BASF, Epiclon 200, Epiclon 400 (above DIC), Epikote 871, Epikote 872 (above is Japan Epoxy Resin), ED-5661, ED-5662 (above Celanese) Cycloester epoxy compound; (Dencol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX -421, an aliphatic polyglycidyl ether compound such as Denacol EX-313, Denacol EX-314, and Denacol EX-312 (manufactured by Nagasechemtex Co., Ltd.).

環被平均3.7個甲氧基甲基取代之MX-750、每1個三

環被平均5.8個甲氧基甲基取代之MW-30(以上為(股)Sanwa-Chemical製)；Cymel 300、Cymel 301、Cymel 303、Cymel 350、Cymel 370、Cymel 771、Cymel 325、Cymel 327、Cymel 703、Cymel 712等甲氧基甲基化三聚氰胺；Cymel 235、Cymel 236、Cymel 238、Cymel 212、Cymel 253、Cymel 254等甲氧基甲基化丁氧基甲基化三聚氰胺；Cymel 506、Cymel 508等丁氧基甲基化三聚氰胺；Cymel 1141般含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺；Cymel 1123般甲氧基甲基化乙氧基甲基化苯胍胺；Cymel 1123-10般甲氧基甲基化丁氧基甲基化苯胍胺；Cymel 1128般丁氧基甲基化苯胍胺；Cymel 1125-80般含有羧基之甲氧基甲基化乙氧基甲基化苯胍胺；Cymel 1170般丁氧基甲基化甘脲；Cymel 1172般羥甲基化甘脲(以上為Mitsui Cyanamid(股)製)等。 The melamine derivative, the benzoguanamine derivative or the glycoluril having a hydrogen atom having an amine group which is substituted by a methylol group, an alkoxymethyl group or both, for example: one for each three

Ring is replaced by an average of 3.7 methoxymethyl MX-750, one per three

MW-30 (manufactured by Sanwa-Chemical) with an average of 5.8 methoxymethyl groups; Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327 , methoxymethylated melamine such as Cymel 703, Cymel 712; methoxymethylated butoxymethylated melamine such as Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254; Cymel 506, Cymel 508 and other butoxymethylated melamine; Cymel 1141-like carboxylated methoxymethylated isobutoxymethylated melamine; Cymel 1123-like methoxymethylated ethoxymethylated benzoguanamine Cymel 1123-10-like methoxymethylated butoxymethylated benzoguanamine; Cymel 1128-like butoxymethylated benzoguanamine; Cymel 1125-80-like carboxylated methoxymethylated B Oxymethylated benzoguanamine; Cymel 1170-like butoxymethylated glycoluril; Cymel 1172-like methylolated glycoluril (manufactured by Mitsui Cyanamid Co., Ltd.) and the like.

Further, in the resin composition for a display substrate of the present invention, from the viewpoint of improving the storage stability of the resin composition, it is based on polyglycine or polyamidiamine (including both polyglycine and 100 parts by mass of the polyimine), the content of the crosslinking agent is preferably 20 parts by mass or less; and the cured film obtained by the resin composition of the present invention has a sufficiently low coefficient of linear expansion, cross-linking The content of the agent is more preferably 15 parts by mass or less.

[varnish and hardened film]

A specific method of forming a cured film using the resin composition for a display substrate of the present invention is as follows.

First, the polyamic acid containing the structural unit represented by the formula (1) and the structural unit represented by the formula (3) or the structural unit represented by the above formula (2) and the formula (4) are used. The polyimine of the structural unit shown is dissolved or dispersed in a solvent, and a resin composition is produced in the form of a varnish (film forming material). Alternatively, the reaction solution of polylysine or polyimine described above may be used as it is, or by diluting or concentrating, a resin composition in the form of a varnish may be prepared.

Next, the varnish is subjected to a spin coating method, a knife coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, a printing method (embossing, gravure, lithography) , screen printing, etc.) are applied to the substrate to obtain a coating film. Then, the obtained coating film is fired by a hot plate, an oven, or the like to form a cured film.

The calcination temperature for forming the cured film is generally from 100 to 400 ° C, preferably from 100 to 350 ° C, whereby the solvent is evaporated by the calcination, and the poly-proline is dehydrated and closed (醯i-imidized) to become a poly Yttrium. In this case, in order to exhibit a higher uniform film formability, it is also possible to impart a temperature change of two or more stages for the purpose of allowing the reaction to proceed on the substrate.

Further, examples of the substrate to be used include plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene). Resin), metal, wood, paper, glass, slate, etc.

The solvent to be used in the form of the above-mentioned varnish is not particularly limited as long as it can dissolve or disperse the polyaminic acid or the polyimine, and for example, it is used in the formation reaction of the polyamic acid. Solvents, etc. These solvents may be used alone or in combination of two or more.

Further, a concentration of polylysine or polyamidiamine (polyamide and polyimine in both cases, the same applies hereinafter) dissolved or dispersed in the above solvent It is preferably 5 to 40% by mass based on the total mass (total mass) of the polyaminic acid or the polyimide and the solvent, and is preferably 5 to 5 in terms of improving the storage stability of the resin composition. 20% by mass; more preferably 5 to 15% by mass from the viewpoint of improving the coatability of the varnish.

The thickness of the cured film formed of the resin composition for a display substrate is not particularly limited, but is generally 1 to 50 μm, preferably 5 to 40 μm.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples.

[Description of the code used in the examples]

The symbols used in the following examples have the following meanings.

<acid dianhydride>

BP-TME: 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (manufactured by Honshu Chemical Industry Co., Ltd.) (Formula (11) below)

TAHQ: p-phenylene bis(trimellitic acid monoester anhydride) (manac (manufactured by Manac)) ((Formula (12) below)

<Diamine>

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

APABI: 2-(3-aminophenyl)-5-aminobenzimidazole (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.)

BABP: 4,4'-bis(3-aminophenoxy)benzophenone (manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.)

BAPB: 4,4'-bis(4-aminophenoxy)biphenyl (Tokyo Chemical Co., Ltd.)

<crosslinker>

V8000-C7: naphthalene epoxy compound (made by DIC)

<solvent>

NMP: N-methylpyrrolidone

[Measurement of number average molecular weight and weight average molecular weight]

The weight average molecular weight (hereinafter referred to as Mw) and the molecular weight distribution of the polymer are GPC apparatus (Shodex [registered trademark] column KF803L and KF805L) manufactured by JASCO Corporation, and dimethylformamide is used as a dissolution solvent. The measurement was carried out under the conditions of a flow rate of 1 mL/min and a column temperature of 50 °C. Still, Mw is a value converted to polystyrene.

<Synthesis Example P1: Synthesis of Polyproline (P1)>

1.66 g (0.015 mol) of PDA and APABI 0.862 g (0.004 mol) were dissolved in NMP 70 g, BP-TME 10.1 g (0.019 mol) was added, and then NMP 7.4 g was added, under nitrogen atmosphere, 23 ° C The reaction was allowed to proceed for 24 hours. The obtained polymer had a Mw of 134,000 and a molecular weight distribution of 2.8.

<Synthesis Example P2: Synthesis of Polylysine (P2)>

PDA 1.82g (0.017 mol) and APABI 0.42g (0.002 mol) were dissolved in NMP 80g, BP-TME 9.77g (0.018 mol) was added, and then NMP 8g was added, and the nitrogen atmosphere was made at 23 ° C. Reaction for 24 hours. The obtained polymer had a Mw of 138,600 and a molecular weight distribution of 2.3.

<Synthesis Example P3: Synthesis of Polyproline (P3)>

1.32 g (0.013 mol), APABI 0.16 g (0.001 mol) and BABP 0.6 g (0.002 mol) were dissolved in NMP 70 g, BP-TME 8.78 g (0.016 mol) was added, and then NMP 9.2 was added. g, the reaction was allowed to proceed at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 151,400 and a molecular weight distribution of 2.8.

<Synthesis Example P4: Synthesis of Polyproline (P4)>

PDA 1.42g (0.013 mole), APABI 0.16g (0.001 mole) After dissolving 0.5 g of BAPB (0.002 mol) in 70 g of NMP and adding 7.36 g (0.014 mol) of BP-TME, 11.0 g of NMP was further added, and the reaction was allowed to proceed at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 138,600 and a molecular weight distribution of 2.3.

<Comparative Example HP1: Synthesis of Polyproline (HP1)>

22.7 g (0.210 mol) of PDA was dissolved in 700 g of NMP, and after adding TAHQ 94.3 g (0.205 mol), 83 g of NMP was further added, and the reaction was carried out at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 142,700 and a molecular weight distribution of 2.5.

<Comparative Example HP2: Synthesis of Polyproline (HP2)>

APABI 3.78 g (0.017 mol) was dissolved in 70 g of NMP, and after adding 8.82 g (0.017 mol) of BP-TME, 7.4 g of NMP was further added, and the reaction was allowed to proceed at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 148,400 and a molecular weight distribution of 2.5.

<Comparative Example HP3: Synthesis of Polyproline (HP3)>

1.46 g (0.014 mol) of PDA and 2.30 g (0.006 mol) of BABP were dissolved in 70 g of NMP, and 8.79 g (0.019 mol) of BP-TME was added, and then 7.4 g of NMP was added thereto, under a nitrogen atmosphere at 23 ° C. The reaction was allowed to proceed for 24 hours. The obtained polymer had a Mw of 102,000 and a molecular weight distribution of 3.3.

<Comparative Example HP4: Synthesis of Polyaminic Acid (HP4)>

APABI 4.46 g (0.018 mol) was dissolved in 80 g of NMP, TAHQ 8.00 g (0.017 mol) was added, and 8 g of NMP was further added, and the reaction was allowed to proceed at 23 ° C for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 142,700 and a molecular weight distribution of 2.5.

<Production sample: varnish>

According to the composition shown in Table 1, a resin solution for a display substrate was prepared by mixing a polymer solution, a crosslinking agent, and NMP as a solvent, and stirring at room temperature (about 23 ° C) for 6 hours or more to obtain a homogeneous solution. (varnish).

<Coating film and coefficient of linear expansion>

The resin composition (varnish) for the display substrate prepared above was evaluated by the following method. The evaluation results are shown in Table 2.

[film thickness before curing. Stripping method]

Use the bar coater (step difference 250 μm) to use the display substrate of Table 1 The fat composition (varnish) was applied to a glass substrate of 100 mm × 100 mm, and calcined by an oven having a temperature of 110 ° C for 10 minutes, a temperature of 250 ° C for 30 minutes, and a temperature of 300 ° C for 30 minutes. The film thickness of the obtained coating film was measured using a contact type film thickness measuring instrument (Dektak 3ST manufactured by ULVAC). Thereafter, each of the glass substrates was placed in pure water of 70 degrees in a 1 L beaker to carry out film peeling.

〔Linear expansion coefficient〕

A strip of 20 mm × 5 mm was prepared from the film obtained above, and was heated from 50 degrees to 400 degrees at 5 degrees/min using TMA-4000SA (manufactured by Bruker AXS Co., Ltd.), and measured again from 50 degrees to 50 degrees after cooling. Linear expansion coefficient up to 400 degrees. Further, the coefficient of linear expansion is expressed by a coefficient at the low temperature (50 ° C to 300 ° C) side and the high temperature (300 ° C to 400 ° C) side.

As is apparent from the results shown in Table 2, the film obtained from the resin composition for a display substrate of the present invention has a moderate coefficient of linear expansion, moderate flexibility, and sufficient heat resistance.

Claims (19)

A resin composition for a display substrate, comprising a polylysine or a polyimine, wherein the polyamic acid is a structural unit represented by the following formula (1) and a formula (3) In the structural unit, the polyimine is a structural unit represented by the following formula (2) and a structural unit represented by the formula (4). [In the formulae (1) to (4), X ¹ is a tetravalent organic group having an aromatic group and two carbonyl groups represented by the following formula (7), (wherein R ¹² to R ²¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl , W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Or a carboxyl group, Z ¹ and Z ² are each independently shown as -NH-, -NZ ³ - or an oxygen atom, Z ^{3 is} shown as an alkyl group having 1 to 10 carbon atoms, p is 1 or 2, still, ○ a bond bond), Y ¹ is shown by the following formula (6 a divalent aliphatic group or the aromatic group represented by the), (wherein R ⁸ to R ¹¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. a base or a carboxyl group, q is 1 or 2, and ○ is a bond, and Y ² is a divalent aromatic group having two or more nitrogen atoms represented by the following formula (5). (wherein R ¹ to R ⁷ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. A group or a carboxyl group, A is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and ○ is a bond, and n and m are a natural number. The resin composition for a display substrate according to claim 1, wherein the above R ¹ to R ⁷ and A are represented by a hydrogen atom. The resin composition for a display substrate according to claim 1, wherein the divalent aromatic group represented by the above formula (6) is derived from phenylenediamine. The resin composition for a display substrate according to claim 3, wherein the aforementioned R ⁸ to R ¹¹ are represented by a hydrogen atom. The resin composition for a display substrate according to claim 1, wherein the aforementioned p is 2. The resin composition for a display substrate according to claim 5, wherein the aforementioned R ¹² to R ²¹ are represented by a hydrogen atom. The resin composition for a display substrate according to claim 1, wherein n in the above formula (1) and m in the above formula (3) are in a relationship of n/m = 70/30 to 99/1. The resin composition for a display substrate according to claim 1, wherein n in the above formula (2) and m in the above formula (4) are in a relationship of n/m = 70/30 to 99/1. The resin composition for a display substrate of claim 1, which further comprises a crosslinking agent. The resin composition for a display substrate according to claim 9, wherein the crosslinking agent is a compound having two or more epoxy groups. The resin composition for a display substrate according to claim 10, wherein the crosslinking agent is a compound having an aromatic group. The resin composition for a display substrate according to claim 11, wherein the crosslinking agent is a compound having 6 or less epoxy groups, and the compound has a carbon atom number of 1 to 10 having a bonded epoxy group and an aromatic group. alkyl. The resin composition for a display substrate according to any one of the preceding claims, wherein the crosslinking agent is 20 parts by mass or less based on 100 parts by mass of the polyamic acid or polyimine. A varnish which is a resin composition for a display substrate according to any one of Claims 1 to 13, which is dissolved in at least one solvent. A cured film obtained by using the varnish of claim 14 and calcining at 230 C or more. A structure comprising at least one layer of a cured film as claimed in claim 15 attached to a substrate. a polyamic acid comprising a structural unit represented by the following formula (1) and a structural unit represented by the formula (3), [In the formulae (1) and (3), X ¹ is a tetravalent organic group having an aromatic group and two carbonyl groups represented by the following formula (7), (wherein R ¹² to R ²¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Or a carboxyl group, Z ¹ and Z ² are each independently shown as -NH-, -NZ ³ - or an oxygen atom, Z ^{3 is} shown as an alkyl group having 1 to 10 carbon atoms, p is 1 or 2, still, ○ a bond bond), Y ¹ is shown by the following formula (6 a divalent aliphatic group or the aromatic group represented by the), (wherein R ⁸ to R ¹¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. a base or a carboxyl group, q is 1 or 2, and ○ is a bond, and Y ² is a divalent aromatic group having two or more nitrogen atoms represented by the following formula (5). (wherein R ¹ to R ⁷ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl , W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. A group or a carboxyl group, A is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and ○ is a bond, and n and m are a natural number. a polyimine comprising a structural unit represented by the following formula (2) and a structural unit represented by the formula (4), [In the formulae (2) and (4), X ¹ is an organic group having an aromatic group and a tetravalent carbonyl group represented by the following formula (7), (wherein R ¹² to R ²¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl , W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. Or a carboxyl group, Z ¹ and Z ² are each independently shown as -NH-, -NZ ³ - or an oxygen atom, Z ^{3 is} shown as an alkyl group having 1 to 10 carbon atoms, p is 1 or 2, still, ○ a bond bond), Y ¹ is shown by the following formula (6 a divalent aliphatic group or the aromatic group represented by the), (wherein R ⁸ to R ¹¹ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. a base or a carboxyl group, q is 1 or 2, and ○ is a bond, and Y ² is a divalent aromatic group having two or more nitrogen atoms represented by the following formula (5). (wherein R ¹ to R ⁷ are each independently represented by a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a hydroxyl group; a halogen atom, a nitro group, methyl acyl, cyano, carboxy which may be substituted with W ¹ of the phenyl group which may be substituted with W ¹ of the naphthyl group which may be substituted with W ¹ or the thienyl which may be substituted with W ¹ of furanyl W ^{1 is} shown as an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, a decyl group, and a cyanogen group. A group or a carboxyl group, A is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a haloalkyl group having 1 to 10 carbon atoms, and ○ is a bond, and n and m are a natural number. A substrate for a display formed by the polyimine of claim 18.