WO2017164129A1

WO2017164129A1 - Polyhydroxyamide composition for manufacturing substrate for electronic device, and polybenzoxazole resin film

Info

Publication number: WO2017164129A1
Application number: PCT/JP2017/010970
Authority: WO
Inventors: 和也進藤; 江原　和也
Original assignee: 日産化学工業株式会社
Priority date: 2016-03-22
Filing date: 2017-03-17
Publication date: 2017-09-28
Also published as: KR20210100761A; JP2021178962A; TWI774667B; JPWO2017164129A1; KR20180127376A; TW201802184A; KR102382236B1; CN108884316A; CN108884316B; JP6904332B2

Abstract

Provided is a polyhydroxyamide composition for manufacturing a substrate for an electronic device, the composition including: (A) a polyhydroxyamide containing a unit represented by formula (1) and a unit represented by formula (2); and (B) an organic solvent. [In the formulae, X¹ represents a biphenyldiyl group having a hydroxy group on a carbon atom adjacent to a carbon atom bonded to a nitrogen atom; Y¹ represents a divalent aromatic group having 6-14 carbon atoms; Y² represents a group represented by formula (3); and n and m each represent an integer satisfying 0<n<100, 0<m<100, and 0<n+m≤100. (In the formula, Z¹ represents -O-, -NH-, or -N(R)-; R represents an alkyl group having 1-10 carbon atoms; Ar¹ and Ar² each independently represent a divalent aromatic group having 6-14 carbon atoms; and the dashed lines represent bonds.)]

Description

Polyhydroxyamide composition for manufacturing substrates for electronic devices, and polybenzoxazole resin film

The present invention relates to a polyhydroxyamide composition for producing a substrate for an electronic device, and a polybenzoxazole resin film obtained from the composition.

In recent years, with the progress of miniaturization and high performance of electronic devices, characteristics such as lightness and heat resistance are also demanded for members used in electronic devices. In particular, in the field of organic electroluminescence (EL) displays, glass members may occupy most of the weight of the equipment, and the expectations for flexible displays in the market are increasing. There is a great demand for alternative materials with flexibility.

Glass has excellent heat resistance and low coefficient of linear expansion, so it is used as a member for electronic equipment. Therefore, excellent heat resistance and a low coefficient of linear expansion are also required for new materials replacing glass. In particular, in a manufacturing process of a high-definition display or the like, it is necessary to process at a high temperature of 200 ° C. or higher, and in some cases 400 ° C. or higher while maintaining high dimensional accuracy. It is essential to be excellent in terms of characteristics.

From this point of view, polyimide resins are attracting attention as candidates for new materials because of their high heat resistance, flame retardancy and excellent electrical insulation. However, generally used polyimide resins do not have a sufficiently low linear expansion coefficient to the extent that high dimensional accuracy can be maintained even under high temperature processing, and therefore, in the display manufacturing process, the resin shrinks (or expands). ) May not be possible at high temperatures. In view of such circumstances, a polyimide having a low linear expansion coefficient using a technology related to a manufacturing method of a display element that does not include heat treatment at a temperature at which the polyimide resin shrinks (or expands), and a characteristic acid dihydrate. Technologies related to resins have been proposed (Patent Documents 1 and 2).

However, even when such a technique is used, there are problems such as complicated manufacturing processes and the need to use expensive acid dihydrates with poor versatility, as well as flexible displays and the like. It is difficult to achieve sufficient flexibility for use in applications. For this reason, it is difficult to solve these points with the conventional polyimide resin, and an alternative material is required.

On the other hand, there is polybenzoxazole resin as a material having heat resistance and low linear expansion coefficient equal to or higher than those of polyimide (Non-patent Document 1). However, polyhydroxyamide, which is a precursor of polybenzoxazole, has a problem that it is less soluble than polyamic acid, which is a precursor of polyimide, and precipitates during synthesis or is difficult to redissolve after purification. For this reason, in order to impart solubility, a technique for protecting a side chain hydroxy group with a silyl group, using hexamethylphosphoric triamide as a solvent, or performing copolymerization with a polyamic acid has been reported (Non-Patent Literature). 1 to 3, Patent Document 3). However, silylating agents are expensive, and hexamethylphosphoric triamide is highly toxic and therefore lacks industrial applicability. Further, the copolymerization with polyamic acid has a drawback of poor heat resistance.

JP 2001-356370 A International Publication No. 2008/047591 JP 2009-109541 A

The present invention has been made in view of the above circumstances, and provides a polyhydroxyamide composition capable of providing a polybenzoxazole resin film having high heat resistance, and a polybenzoxazole resin film obtained from the composition. Objective.

As a result of intensive studies to achieve the above object, the present inventors have found that a polyhydroxyamide containing a unit represented by the following formula (1) and a unit represented by the following formula (2), and (B ) A polybenzoxazole resin film obtained from a composition containing an organic solvent was found to have high heat resistance and a low linear expansion coefficient, and the present invention was completed.

Accordingly, the present invention provides the following polyhydroxyamide composition for producing a substrate for an electronic device and a polybenzoxazole resin film.
1. (A) A polyhydroxyamide composition for producing a substrate for electronic devices, comprising a unit represented by the following formula (1) and a polyhydroxyamide containing a unit represented by the following formula (2), and (B) an organic solvent.

[Wherein, X ¹ represents a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom; Y ¹ represents a divalent aromatic group having 6 to 14 carbon atoms] Y ² represents a group represented by the following formula (3); n and m represent positive numbers satisfying 0 <n <100, 0 <m <100, and 0 <n + m ≦ 100.

(Wherein Z ¹ represents —O—, —NH— or —N (R) —, R represents an alkyl group having 1 to 10 carbon atoms; Ar ¹ and Ar ² are independently of each other; Represents a divalent aromatic group having 6 to 14 carbon atoms; a broken line represents a bond.)]
2. A polyhydroxyamide composition for producing a substrate for an electronic device according to 1, wherein X ¹ is a group represented by the following formula (4):

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; a broken line represents a bond.)
3. A polyhydroxyamide composition for producing a substrate for an electronic device according to 2, wherein X ¹ is a group represented by the following formula (4 ′).

(In the formula, a broken line represents a bond.)
4). The polyhydroxyamide composition for producing a substrate for an electronic device according to any one of 1 to 3, wherein Y ¹ is a group represented by the following formula (5) and Y ² is a group represented by the following formula (6).

Wherein Z ¹ is as defined above; R ⁷ to R ¹⁸ may be independently of each other substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom. Preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; A broken line represents a bond.)
5. 4. A polyhydroxyamide composition for producing a substrate for an electronic device, wherein R ⁷ to R ¹⁸ are hydrogen atoms.
6). The polyhydroxyamide composition for producing a substrate for an electronic device according to any one of 1 to 5, wherein Y ² is a group represented by the following formula (7), (8) or (9):

(In the formula, a broken line represents a bond.)
7). The polyhydroxyamide composition for producing a substrate for an electronic device according to any one of 1 to 6, wherein n and m are positive numbers satisfying 5 ≦ n ≦ 25, 75 ≦ m ≦ 95, and 80 ≦ n + m ≦ 100.
8). (B) The organic solvent contains at least one selected from amides represented by the following formula (S1), amides represented by the following formula (S2), and amides represented by the following formula (S3). The polyhydroxyamide composition for a substrate for electronic devices according to any one of 1 to 7.

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms. R ²³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A is a natural number. Represents.)
9. An electronic device comprising: a step of applying a polyhydroxyamide composition for producing a substrate for an electronic device according to any one of 1 to 8 on a substrate; and a step of heating to evaporate a solvent and ring-closing the polyhydroxyamide A method for producing a polybenzoxazole resin film for a substrate.
10. A polybenzoxazole resin film for an electronic device substrate obtained from the polyhydroxyamide composition according to any one of 10.1 to 8.
10. A polybenzoxazole resin film for an electronic device substrate, having a 11.5% weight loss temperature of 600 ° C. or more and a linear expansion coefficient of 50 to 400 ° C. of 8 ppm / ° C. or less.
12. An electronic device comprising as a substrate the polybenzoxazole resin film for a substrate for electronic devices according to 10.10 or 11.
13. 12 electronic devices which are organic EL elements.
14 A polyhydroxyamide containing a unit represented by the following formula (10) and a unit represented by the following formula (11).

[Wherein, X ¹ represents a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom; Y ¹ represents a divalent aromatic group having 6 to 14 carbon atoms] Y ² represents a group represented by the following formula (3); n and m represent positive numbers satisfying 5 ≦ n ≦ 25, 75 ≦ m ≦ 95, and 80 ≦ n + m ≦ 100.

(Wherein Z ¹ represents —O—, —NH— or —N (R) —, R represents an alkyl group having 1 to 10 carbon atoms; Ar ¹ and Ar ² are independently of each other; Represents a divalent aromatic group having 6 to 14 carbon atoms; a broken line represents a bond.)]
15. 14 polyhydroxyamides wherein X ¹ is a group represented by the following formula (4).

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; a broken line represents a bond.)
16. 15 polyhydroxyamides wherein X ¹ is a group represented by the following formula (4 ′).

(In the formula, a broken line represents a bond.)
17. The polyhydroxyamide according to any one of 14 to 16, wherein Y ¹ is a group represented by the following formula (5), and Y ² is a group represented by the following formula (6).

Wherein Z ¹ is as defined above; R ⁷ to R ¹⁸ may be independently of each other substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom. Preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; A broken line represents a bond.)
18. 17 polyhydroxyamides in which R ⁷ to R ¹⁸ are hydrogen atoms;
19. The polyhydroxyamide according to any one of 14 to 18, wherein Y ² is a group represented by the following formula (7), (8) or (9).

(In the formula, a broken line represents a bond.)
20. A diamine compound represented by the following formula (12), a dicarboxylic acid derivative represented by the following formula (13) in an amount of 0.05 to 0.25 mol relative to 1 mol of the diamine compound, and the diamine compound 1 A method for producing a polyhydroxyamide, comprising subjecting a dicarboxylic acid derivative represented by the following formula (14) in an amount of 0.75 to 0.95 mole to the mole to condensation polymerization in a solvent in the presence of a catalyst.

[Wherein, X ¹ represents a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom; Y ¹ represents a divalent aromatic group having 6 to 14 carbon atoms] ; Y ² represents a group represented by the following formula (3).

(Wherein Z ¹ represents —O—, —NH— or —N (R) —, R represents an alkyl group having 1 to 10 carbon atoms; Ar ¹ and Ar ² are independently of each other; Represents a divalent aromatic group having 6 to 14 carbon atoms; a broken line represents a bond.)]
21. A method for producing 20 polyhydroxyamides, wherein X ¹ is a group represented by the following formula (4).

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; a broken line represents a bond.)
22. 21. A method for producing a polyhydroxyamide according to 21, wherein X ¹ is a group represented by the following formula (4 ′).

(In the formula, a broken line represents a bond.)
23. A method for producing a polyhydroxyamide according to any one of 20 to 22, wherein Y ¹ is a group represented by the following formula (5) and Y ² is a group represented by the following formula (6).

Wherein Z ¹ is as defined above; R ⁷ to R ¹⁸ may be independently of each other substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom. Preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; A broken line represents a bond.)
24. A method for producing a polyhydroxyamide of 23, wherein R ⁷ to R ¹⁸ are hydrogen atoms.
25. A process for producing a polyhydroxyamide according to any one of 20 to 24, wherein Y ² is a group represented by the following formula (7), (8) or (9).

(In the formula, a broken line represents a bond.)

The polybenzoxazole resin film obtained from the polyhydroxyamide composition of the present invention has high heat resistance and a low linear expansion coefficient. Therefore, the polybenzoxazole resin film is useful as a substrate for electronic devices.

[Polyhydroxyamide composition for manufacturing substrates for electronic devices]
The polyhydroxyamide composition for producing a substrate for an electronic device of the present invention comprises (A) a polyhydroxyamide having a predetermined structure, and (B) an organic solvent.

[(A) Polyhydroxyamide]
The polyhydroxyamide as the component (A) includes a unit represented by the following formula (1) and a unit represented by the following formula (2).

In the formula, X ¹ is a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom.

Specifically, X ¹ is preferably a group represented by the following formula (4).

In the formula, R ¹ to R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or 2 carbon atoms Represents an alkenyl group having 20 carbon atoms, an alkynyl group having 2-20 carbon atoms, an aryl group having 6-20 carbon atoms, or a heteroaryl group having 2-20 carbon atoms. A broken line represents a bond.

The alkyl group may be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl Group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n- Propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-silane Ropropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n -Butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2- Trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1 -Methyl-cyclopentyl group, 2-methyl-cyclopentyl Group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2, 2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl- Cyclopropyl group, 1-isopropyl-cyclopropyl group, 2-isopropyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3- Trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl Examples thereof include a til-2-methyl-cyclopropyl group and a 2-ethyl-3-methyl-cyclopropyl group.

The alkenyl group may be linear, branched or cyclic, and specific examples thereof include ethenyl group, n-1-propenyl group, n-2-propenyl group, 1-methylethenyl group, n-1- Butenyl group, n-2-butenyl group, n-3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1 -Methyl-2-propenyl group, n-1-pentenyl group, n-1-decenyl group, n-1-eicocenyl group and the like.

The alkynyl group may be linear, branched or cyclic, and specific examples thereof include ethynyl group, n-1-propynyl group, n-2-propynyl group, n-1-butynyl group, n- 2-butynyl group, n-3-butynyl group, 1-methyl-2-propynyl group, n-1-pentynyl group, n-2-pentynyl group, n-3-pentynyl group, n-4-pentynyl group, 1 -Methyl-n-butynyl group, 2-methyl-n-butynyl group, 3-methyl-n-butynyl group, 1,1-dimethyl-n-propynyl group, n-1-hexynyl group, n-1-decynyl group N-1-pentadecynyl group, n-1-eicosinyl group and the like.

Specific examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group. Group, 4-phenanthryl group, 9-phenanthryl group and the like.

Specific examples of the heteroaryl group include 2-thienyl group, 3-thienyl group, 2-furanyl group, 3-furanyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 3-isoxazolyl group, 4-isoxazolyl group, 5-isoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl group, Examples include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group and the like.

Of these, R ¹ to R ⁶ are preferably a hydrogen atom, a methyl group, a halogen atom, or a phenyl group, more preferably a hydrogen atom, a methyl group, or a halogen atom, and most preferably a hydrogen atom.

X ¹ is most preferably a group represented by the following formula (4 ′).

(In the formula, a broken line represents a bond.)

In formula (1), Y ¹ represents a divalent aromatic group having 6 to 14 carbon atoms. In formula (2), Y ² represents a group represented by the following formula (3).

In the formula (3), Z ¹ represents —O—, —NH— or —N (R) —, and R represents an alkyl group having 1 to 10 carbon atoms. Specific examples of the alkyl group represented by R include those described above. Z ¹ is preferably —O— or —NH—.

In formula (3), Ar ¹ and Ar ² each independently represent a divalent aromatic group having 6 to 14 carbon atoms.

Examples of the divalent aromatic group represented by Y ¹ , Ar ¹ and Ar ² include a phenylene group, a naphthylene group, an anthracenediyl group, a phenanthrene diyl group, a biphenyldiyl group, and the like. A part or all of them may be substituted with a substituent.

Y ¹ is preferably a group represented by the following formula (5), and Y ² is preferably a group represented by the following formula (6).

In the formula, Z ¹ is the same as described above. R ⁷ to R ¹⁸ are each independently a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, or 2 carbon atoms Represents an alkenyl group having 20 carbon atoms, an alkynyl group having 2-20 carbon atoms, an aryl group having 6-20 carbon atoms, or a heteroaryl group having 2-20 carbon atoms. A broken line represents a bond. Examples of the alkyl group, alkenyl group, alkynyl group, aryl group and heteroaryl group are the same as those described above.

R ⁷ to R ¹⁸ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogen atom or a phenyl group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a halogen atom, a hydrogen atom, methyl A group and a halogen atom are more preferable, and a hydrogen atom is most preferable.

Y ² is most preferably a group represented by the following formula (7), (8) or (9).

(In the formula, a broken line represents a bond.)

In the formulas (1) and (2), n and m represent positive numbers that satisfy 0 <n <100, 0 <m <100, and 0 <n + m ≦ 100. n and m are preferably positive numbers satisfying 5 ≦ n ≦ 25, 75 ≦ m ≦ 95, and 80 ≦ n + m ≦ 100 from the viewpoint of solubility and heat resistance, and 10 ≦ n ≦ 25, 75 ≦ m ≦ 90. And positive numbers satisfying 85 ≦ n + m ≦ 100 are more preferable, and positive numbers satisfying 20 ≦ n ≦ 25, 75 ≦ m ≦ 80, and 95 ≦ n + m ≦ 100 are even more preferable.

The polyhydroxyamide may include units other than the unit represented by the formula (1) and the unit represented by the formula (2) (hereinafter also referred to as other units).

The weight average molecular weight (Mw) of the polyhydroxyamide is preferably 5,000 to 1,000,000, more preferably 10,000 to 100,000, and even more preferably 20,000 to 100,000. In the present invention, Mw is an average molecular weight obtained by standard polystyrene conversion by gel permeation chromatography (GPC) analysis.

[Production method of polyhydroxyamide]
The polyhydroxyamide contains a diamine compound represented by the following formula (12), a dicarboxylic acid derivative represented by the following formula (13), and a dicarboxylic acid derivative represented by the following formula (14) in a solvent, If necessary, it can be produced by condensation polymerization in the presence of a base.

(In the formula, X ¹ , Y ¹ and Y ² are the same as described above. Hal represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom.)

At this time, the amount of the dicarboxylic acid derivative represented by the formula (13) is preferably 0.05 to 0.25 mol, based on 1 mol of the diamine compound represented by the formula (12). 0.25 mol is more preferable, and 0.20 to 0.25 mol is even more preferable. The amount of the dicarboxylic acid derivative represented by the formula (14) is preferably from 0.75 to 0.95 mol, preferably from 0.75 to 0, per 1 mol of the diamine compound represented by the formula (12). .90 mol is more preferable, and 0.75 to 0.80 mol is even more preferable.

Examples of the solvent used in the condensation polymerization reaction include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, 3 -Methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.

Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, water Barium oxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2 , 6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, N-methylmorpholine and the like. The amount of the base added is preferably 0.5 to 3.0 mol, more preferably 0.8 to 2.0 mol, relative to 1 mol of the diamine compound.

The reaction temperature may be appropriately set in the range from the melting point of the solvent to be used to the boiling point of the solvent, and is usually about −20 to 100 ° C., preferably about −10 to 100 ° C. The polymerization reaction time is usually about 1 to 48 hours, preferably about 1 to 24 hours. After completion of the reaction, the desired product can be obtained by post-treatment according to a conventional method and, if necessary, purification such as reprecipitation.

[(B) Organic solvent]
The organic solvent of component (B) is not particularly limited as long as it can dissolve the polyhydroxyamide, but considering that a highly flat polybenzoxazole resin film can be obtained with good reproducibility, the following formula (S1) And those containing at least one selected from amides represented by the following formula (S2) and amides represented by the following formula (S3).

In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms. R ²³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, Examples thereof include a sec-butyl group and a tert-butyl group.

In the formula (S1), a represents a natural number, preferably a natural number of 1 to 3, more preferably 1 or 2.

Examples of the organic solvent represented by the formula (S1) include 2-methoxy-N, N-dimethylacetamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropylamide, 3- Propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethylpropylamide, 3 -Tert-butoxy-N, N-dimethylpropylamide and the like.

Examples of the organic solvent represented by the formula (S2) include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone and the like. It is done.

Examples of the organic solvent represented by the formula (S3) include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylpropionamide, N, N-dimethylisobutyramide and the like.

Further, even if the solvent alone does not dissolve the polyhydroxyamide, it can be used in addition to the solvent as long as the solubility is not impaired. Specific examples thereof include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and 1-butoxy-2-propanol. 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-Ethoxypropoxy) propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and the like.

In the polyhydroxyamide composition, the concentration of polyhydroxyamide is appropriately set in consideration of the thickness of the resin film to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably 1 About 20% by mass.

[Polybenzoxazole resin film]
The polybenzoxazole resin film of the present invention is obtained from the polyhydroxyamide composition. The method for producing the polybenzoxazole resin film includes a step of applying the polyhydroxyamide composition onto a substrate, and a step of heating to evaporate the solvent and ring-closing the polyhydroxyamide.

Examples of the substrate include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), SiN, Examples thereof include glass substrates with vapor deposition films such as SiO films, wood, paper, slate, etc. From the viewpoint of productivity, glass, metal (silicon wafer, etc.) are particularly preferable. In addition, the base material surface may be comprised with the single material and may be comprised with two or more materials.

The method for applying the polyhydroxyamide composition is not particularly limited, for example, cast coating method, spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method, inkjet method, Examples of the printing method include relief printing, intaglio printing, planographic printing, and screen printing.

The heating temperature for evaporating the organic solvent is preferably 50 to 200 ° C, more preferably 50 to 150 ° C. The heating time at that time is preferably 5 minutes to 5 hours, and more preferably 5 minutes to 3 hours.

At this time, the heating temperature for ring closure is usually appropriately determined within the range of 50 to 550 ° C., but is preferably 200 ° C. or more, and preferably 500 ° C. or less. By setting the heating temperature in this way, it is possible to sufficiently advance the oxazolation reaction while preventing the obtained film from being weakened. The heating time varies depending on the heating temperature, and cannot be generally defined, but is usually 5 minutes to 5 hours. The ring closure rate may be in the range of 50 to 100%.

As a preferred example of the heating mode, after heating at 50 to 100 ° C. for 5 minutes to 2 hours, the heating temperature is gradually raised as it is, and finally heating is performed at a temperature exceeding 375 ° C. to 450 ° C. for 30 minutes to 4 hours. Is mentioned. In particular, after heating at 50 to 100 ° C. for 5 minutes to 2 hours, it is preferable to heat at over 100 ° C. to 375 ° C. for 5 minutes to 2 hours, and finally at over 375 ° C. to 450 ° C. for 30 minutes to 4 hours.

The thickness of the resin film is not particularly limited, but when used as a substrate of an electronic device to be described later, it is usually about 1 to 100 μm, preferably about 5 to 75 μm from the viewpoint of sufficient self-supporting property and flexibility. The thickness is preferably about 5 to 50 μm.

After the resin film is formed, the resin film can be peeled off from the substrate and recovered. The film can be peeled by immersion in water, a laser lift-off method using ultraviolet light having a wavelength of 308 nm, or the like.

The polybenzoxazole resin film of the present invention thus obtained has high heat resistance and a small linear expansion coefficient. Specifically, the polybenzoxazole resin film of the present invention preferably has a 5% weight loss temperature of 600 ° C. or higher and a linear expansion coefficient of 50 to 400 ° C. of 8 ppm / ° C. or lower.

[Electronic device]
The electronic device of the present invention comprises the above-described polybenzoxazole resin film as a substrate. Examples of the electronic device include an organic EL element, a liquid crystal display, an organic EL display, an optical semiconductor (LED) element, electronic paper, a solid-state imaging element, an organic thin film solar cell, a dye-sensitized solar cell, an organic thin film transistor (TFT), and a 3D display. And a touch panel.

An example of a method for manufacturing an electronic device according to the present invention will be described. By the above-mentioned method, the polyhydroxyamide composition is applied on a substrate and heated to form a polybenzoxazole resin film fixed to the substrate. Next, a desired circuit is formed on the resin film, and then the resin film is cut, and the resin film on which the circuit is formed is peeled off from the substrate to form a circuit. By separating the substrate and the substrate, an electronic device can be manufactured.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. In addition, the compound used in the following example and the measuring method of a weight average molecular weight and molecular weight distribution are as follows.

NMP: N-methylpyrrolidone HAB: 4,4′-diamino-3,3′-dihydroxybiphenyl 4BP: 3,3′-diamino-4,4′-dihydroxybiphenyl TPC: terephthalic acid chloride IPC: isophthalic acid chloride DEDC: 4,4'-diphenyl ether dicarboxylic acid chloride

[Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
Mw and Mw / Mn of the polymer are GPC apparatus manufactured by JASCO Corporation (column: Shodex (registered trademark) columns KF803L and KF805L manufactured by Showa Denko KK, elution solvent: dimethylformamide, flow rate: 1.0 mL / min, Column temperature: 50 ° C., Mw: standard polystyrene conversion value).

[1] Synthesis of Polymer [Example 1] Synthesis of polyhydroxyamide P1 1.052 g (12.18 mmol) of pyridine was added to 0.963 g (12.18 mmol) of pyridine after dissolving 1.052 g (4.87 mmol) of HAB in 27.6 g of NMP. 3.90 mmol) and 1.198 g (0.97 mmol) of TPC were added and stirred at room temperature for 24 hours. Thereafter, the obtained solution was poured into 500 mL of pure water. The resulting precipitate was filtered off and dried under reduced pressure at 70 ° C. for 24 hours to obtain the desired polyhydroxyamide P1. According to GPC measurement, Mw of polyhydroxyamide P1 was 60,300, and Mw / Mn was 2.8.

[Example 2, Comparative Examples 1 to 5] Synthesis of polyhydroxyamide P2 and polyhydroxyamides CP1 to CP5 Polyhydroxyamide P2 and polyhydroxyamides CP1 to CP5 were synthesized in the same manner as in Example 1. Table 1 shows the type and amount of dicarboxylic acid chloride used, the type and amount of diamine, the amount of NMP used, Mw, and Mw / Mn.

[2] Evaluation of solubility of polyhydroxyamide 1 g of the produced polyhydroxyamide was placed in 20 g of NMP and stirred at room temperature for 48 hours to be redissolved.
The results are also shown in Table 1. In addition, the evaluation criteria of solubility are as follows.
○: Dissolved during polymerization and re-dissolved after purification.
Δ: Dissolved during polymerization, but not re-dissolved after purification.
X: Precipitates during polymerization.

[2] Preparation and evaluation of polybenzoxazole resin film [pre-cure film thickness / peeling method]
1 g of polyhydroxyamide prepared in Examples 1-2 and Comparative Example 5 was dissolved in 20 mL of NMP to prepare a polyhydroxyamide composition.
Each composition obtained was applied onto a 100 mm × 100 mm glass substrate using a bar coater and baked on a hot plate at 80 ° C. for 30 minutes. Thereafter, heating is performed at 140 ° C. for 30 minutes, the heating temperature is raised to 210 ° C. (10 ° C./minute, the same applies hereinafter), the heating temperature is raised to 210 ° C. for 30 minutes, the heating temperature is raised to 300 ° C., and 300 ° C. for 30 minutes. The heating temperature was raised to 400 ° C. and heated at 400 ° C. for 60 minutes. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven. The film thickness of the obtained coating film was measured with a contact-type film thickness measuring device (Dektak 3ST manufactured by ULVAC). Table 2 shows the measurement results of the film thickness. Thereafter, the glass substrate was allowed to stand in 70 ° C. pure water in a 1 L beaker, and the film was peeled off.

[Linear expansion coefficient]
A strip of 20 mm × 5 mm was prepared from the obtained film, and the temperature was raised from 50 ° C. to 400 ° C. under the condition of 10 ° C./min using TMA-4000SA (manufactured by Bruker AXS Co., Ltd.) The linear expansion coefficient was measured. The results are shown in Table 2.

[5% weight loss temperature]
A 20 mm x 3 mm strip was prepared from the obtained film, and the weight loss was measured from 50 ° C to 600 ° C using TGA-DTA-2000SR (Bruker AXS Co., Ltd.). The temperature was confirmed. The results are shown in Table 2. In addition, when not reducing the weight by 5% at 600 ° C., it was described as 600 ° C. <.

[Self-supporting]
After the produced film was peeled and then bent 90 ° in all directions, a film having no particular change was regarded as having self-supporting properties.
The results are shown in Table 2. The evaluation criteria for self-supporting properties are as follows.
○: Self-supporting. Even if it bends to 90 degrees, it does not crack. △: Self-supporting, but breaks when bent. ×: No self-supporting. XX: Decomposes on substrate

Claims

(A) A polyhydroxyamide composition for producing a substrate for electronic devices, comprising a unit represented by the following formula (1) and a polyhydroxyamide containing a unit represented by the following formula (2), and (B) an organic solvent.

[Wherein, X 1 represents a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom; Y 1 represents a divalent aromatic group having 6 to 14 carbon atoms] Y 2 represents a group represented by the following formula (3); n and m represent positive numbers satisfying 0 <n <100, 0 <m <100, and 0 <n + m ≦ 100.

(Wherein Z 1 represents —O—, —NH— or —N (R) —, R represents an alkyl group having 1 to 10 carbon atoms; Ar 1 and Ar 2 are independently of each other; Represents a divalent aromatic group having 6 to 14 carbon atoms; a broken line represents a bond.)]
The polyhydroxyamide composition for producing a substrate for an electronic device according to claim 1, wherein X 1 is a group represented by the following formula (4).

(Wherein R 1 to R 6 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; a broken line represents a bond.)
The polyhydroxyamide composition for producing a substrate for an electronic device according to claim 2, wherein X 1 is a group represented by the following formula (4 ′).

(In the formula, a broken line represents a bond.)
The poly for manufacturing a substrate for an electronic device according to any one of claims 1 to 3, wherein Y 1 is a group represented by the following formula (5), and Y 2 is a group represented by the following formula (6): Hydroxyamide composition.

Wherein Z 1 is as defined above; R 7 to R 18 may be independently of each other substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom. Preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; A broken line represents a bond.)
The polyhydroxyamide composition for producing a substrate for an electronic device according to claim 4, wherein R 7 to R 18 are hydrogen atoms.
6. The polyhydroxyamide composition for producing a substrate for an electronic device according to claim 1, wherein Y 2 is a group represented by the following formula (7), (8) or (9).

(In the formula, a broken line represents a bond.)
The polyhydroxyamide for producing a substrate for an electronic device according to any one of claims 1 to 6, wherein n and m are positive numbers satisfying 5≤n≤25, 75≤m≤95, and 80≤n + m≤100. Composition.
(B) The organic solvent contains at least one selected from amides represented by the following formula (S1), amides represented by the following formula (S2), and amides represented by the following formula (S3). The polyhydroxyamide composition for a substrate for an electronic device according to any one of claims 1 to 7.

(In the formula, R 21 and R 22 each independently represent an alkyl group having 1 to 10 carbon atoms. R 23 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. A is a natural number. Represents.)
A step of applying the polyhydroxyamide composition for producing a substrate for an electronic device according to any one of claims 1 to 8 on a substrate, and a step of heating to evaporate the solvent and ring-closing the polyhydroxyamide. A method for producing a polybenzoxazole resin film for a substrate for electronic devices.
A polybenzoxazole resin film for an electronic device substrate obtained from the polyhydroxyamide composition according to any one of claims 1 to 8.
11. The polybenzoxazole resin film for an electronic device substrate according to claim 10, wherein the 5% weight loss temperature is 600 ° C. or more, and the linear expansion coefficient at 50 to 400 ° C. is 8 ppm / ° C. or less.
An electronic device provided with the polybenzoxazole resin film for a substrate for electronic devices according to claim 10 or 11 as a substrate.
The electronic device according to claim 12, which is an organic electroluminescence element.
A polyhydroxyamide containing a unit represented by the following formula (10) and a unit represented by the following formula (11).

[Wherein, X 1 represents a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom; Y 1 represents a divalent aromatic group having 6 to 14 carbon atoms] Y 2 represents a group represented by the following formula (3); n and m represent positive numbers satisfying 5 ≦ n ≦ 25, 75 ≦ m ≦ 95, and 80 ≦ n + m ≦ 100.

(Wherein Z 1 represents —O—, —NH— or —N (R) —, R represents an alkyl group having 1 to 10 carbon atoms; Ar 1 and Ar 2 are independently of each other; Represents a divalent aromatic group having 6 to 14 carbon atoms; a broken line represents a bond.)]
The polyhydroxyamide according to claim 14, wherein X 1 is a group represented by the following formula (4).

(Wherein R 1 to R 6 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; a broken line represents a bond.)
16. The polyhydroxyamide according to claim 15, wherein X 1 is a group represented by the following formula (4 ′).

(In the formula, a broken line represents a bond.)
The polyhydroxyamide according to any one of claims 14 to 16, wherein Y 1 is a group represented by the following formula (5), and Y 2 is a group represented by the following formula (6).

Wherein Z 1 is as defined above; R 7 to R 18 may be independently of each other substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom. Preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; A broken line represents a bond.)
The polyhydroxyamide according to claim 17, wherein R 7 to R 18 are hydrogen atoms.
The polyhydroxyamide according to any one of claims 14 to 18, wherein Y 2 is a group represented by the following formula (7), (8) or (9).

(In the formula, a broken line represents a bond.)
A diamine compound represented by the following formula (12), a dicarboxylic acid derivative represented by the following formula (13) in an amount of 0.05 to 0.25 mol relative to 1 mol of the diamine compound, and the diamine compound 1 A method for producing a polyhydroxyamide, comprising subjecting a dicarboxylic acid derivative represented by the following formula (14) in an amount of 0.75 to 0.95 mole to the mole to condensation polymerization in a solvent in the presence of a catalyst.

[Wherein, X 1 represents a biphenyldiyl group having a hydroxy group on the carbon atom adjacent to the carbon atom bonded to the nitrogen atom; Y 1 represents a divalent aromatic group having 6 to 14 carbon atoms] ; Y 2 represents a group represented by the following formula (3).

(Wherein Z 1 represents —O—, —NH— or —N (R) —, R represents an alkyl group having 1 to 10 carbon atoms; Ar 1 and Ar 2 are independently of each other; Represents a divalent aromatic group having 6 to 14 carbon atoms; a broken line represents a bond.)]
X 1 The method for producing a polyhydroxy amide according to claim 20, wherein a group represented by the following formula (4).

(Wherein R 1 to R 6 are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, Represents an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; a broken line represents a bond.)
The method for producing a polyhydroxyamide according to claim 21, wherein X 1 is a group represented by the following formula (4 ').

(In the formula, a broken line represents a bond.)
The method for producing a polyhydroxyamide according to any one of claims 20 to 22, wherein Y 1 is a group represented by the following formula (5), and Y 2 is a group represented by the following formula (6).

Wherein Z 1 is as defined above; R 7 to R 18 may be independently of each other substituted with a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, a cyano group, or a halogen atom. Preferably represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 2 to 20 carbon atoms; A broken line represents a bond.)
The method for producing a polyhydroxyamide according to claim 23, wherein R 7 to R 18 are hydrogen atoms.
The method for producing a polyhydroxyamide according to any one of claims 20 to 24, wherein Y 2 is a group represented by the following formula (7), (8) or (9).

(In the formula, a broken line represents a bond.)