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

Abstract

To provide a polyhydroxyamide composition which enables production of a polybenzoxazole resin film having high heat resistance, and a polybenzoxazole resin film obtained from the composition.SOLUTION: A polyhydroxyamide composition for manufacturing a substrate for an electronic device contains (A) polyhydroxyamide including 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 onto a carbon atom adjacent to a carbon atom coupled to a nitrogen atom; Y1 represents a divalent aromatic group having 6 to 14 carbon atoms; Y2 represents a structural unit in which two mutually independent divalent aromatic groups having 6 to 14 carbon atoms are coupled to each other through -O-, -NH- or -N(R)-; and n and m represent integers satisfying 0<n<100, 0<m<100 and 0<n+m≤100.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polyhydroxyamide composition for producing substrates for electronic devices, and a polybenzoxazole resin film obtained from the composition. [Background technology]

[0002] In recent years, as electronic devices become smaller and more sophisticated, the materials used in these devices are also required to have properties such as lightness and heat resistance. In particular, in fields such as organic electroluminescence (EL) displays, not only are glass materials often the majority of the weight of the device, but expectations for flexible displays are also increasing in the market, so there is a great demand for new flexible materials to replace glass.

[0003] Glass is used as a component of electronic devices because it has excellent heat resistance and a low coefficient of linear expansion. Therefore, new materials to replace glass also need to have excellent heat resistance and a low coefficient of linear expansion. In particular, in the manufacturing process of high-definition displays, etc., it is necessary to process at high temperatures of 200°C or more, and in some cases even 400°C or more, while maintaining high dimensional accuracy, so it is essential that components such as substrates have excellent properties.

[0004] From this perspective, polyimide resins have attracted attention as candidates for new materials because they have high heat resistance, flame retardancy, and excellent electrical insulation. However, commonly used polyimide resins do not have a sufficiently low linear expansion coefficient to maintain high dimensional accuracy even under high-temperature treatment, and therefore, in the display manufacturing process, there are cases where treatment at a high temperature at which the resin shrinks (or expands) cannot be performed. In view of this situation, techniques have been proposed for manufacturing display elements that do not involve heat treatment at a temperature at which the polyimide resin shrinks (or expands), and for polyimide resins with a low linear expansion coefficient that use a characteristic acid dihydrate (Patent Documents 1 and 2).

[0005] However, even when such a technique is used, there are problems such as a complicated manufacturing process and the necessity to use an expensive acid dihydrate with poor versatility, and it is difficult to achieve sufficient flexibility for use in flexible displays, etc. For this reason, it is difficult to solve these problems with conventional polyimide resins, and alternative materials were needed.

[0006] On the other hand, polybenzoxazole resin is a material having heat resistance and a low linear expansion coefficient similar to or higher than polyimide (Non-Patent Document 1). However, polyhydroxyamide, which is a precursor of polybenzoxazole, is less soluble than polyamic acid, which is a precursor of polyimide, and has problems such as precipitation during synthesis or difficulty in redissolving after purification. For this reason, in order to impart solubility, techniques have been reported in which the side chain hydroxyl group is protected with a silyl group, hexamethylphosphoric triamide is used as a solvent, or copolymerization with polyamic acid is performed (Non-Patent Documents 1-3, Patent Document 3). However, the silylating agent is expensive, and hexamethylphosphoric triamide is highly toxic, so that industrial applicability is poor. In addition, copolymerization with polyamic acid has the disadvantage of poor heat resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2001-356370 A [Patent Document 2] International Publication No. 2008 / 047591 [Patent Document 3] JP 2009-109541 A [Non-patent literature]

[0008] [Non-Patent Document 1] Japan Institute of Electronics Packaging 9 [1] 48-51 (2006) [Non-Patent Document 2] J. Photopolym. Sci. Technol., 17, 2, 2004, 253-258 [Non-Patent Document 3] MACROMOL. Chem. Phys. 2001, 201, 2251-2256 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a polyhydroxyamide composition capable of giving a polybenzoxazole resin film having high heat resistance, and a polybenzoxazole resin film obtained from the composition. [Means for solving the problem]

[0010] Means for Solving the Problems The present inventors have conducted extensive research to achieve the above object, and as a result have found that a polybenzoxazole resin film obtained from a composition containing a polyhydroxyamide containing a unit represented by the formula (1) described below and a unit represented by the formula (2) below, and (B) an organic solvent, has high heat resistance and a small linear expansion coefficient, and have completed the present invention.

[0011] Therefore, the present invention provides the following polyhydroxyamide composition for producing a substrate for an electronic device, and polybenzoxazole resin film. 1. A polyhydroxyamide composition for producing a substrate for an electronic device, comprising: (A) a polyhydroxyamide containing a unit represented by the following formula (1) and a unit represented by the following formula (2); and (B) an organic solvent. [ka] [In the formula, 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 2represents 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.

Chemical Formula

Chemical Formula

Chemical Formula

Chemical Formula

[0012] The polybenzoxazole resin film obtained from the polyhydroxyamide composition of the present invention has high heat resistance and a small linear expansion coefficient, and is therefore useful as a substrate for electronic devices. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] [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 given structure and (B) an organic solvent.

[0014] [(A) Polyhydroxyamide] The polyhydroxyamide which is the component (A) contains a unit represented by the following formula (1) and a unit represented by the following formula (2). [ka]

[0015] 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.

[0016] X 1 Specifically, a group represented by the following formula (4) is preferred. [ka]

[0017] In the formula, R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom. A dashed line represents a bond.

[0018] The alkyl group may be linear, branched, or cyclic. 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, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2 ... n-hexyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl -n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclo butyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,Examples of the cyclopropyl group include a 3-trimethylcyclopropyl group, a 1-ethyl-2-methylcyclopropyl group, a 2-ethyl-1-methylcyclopropyl group, a 2-ethyl-2-methylcyclopropyl group, and a 2-ethyl-3-methylcyclopropyl group.

[0019] The alkenyl group may be linear, branched, or cyclic, and specific examples thereof include ethenyl, n-1-propenyl, n-2-propenyl, 1-methylethenyl, n-1-butenyl, n-2-butenyl, n-3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, n-1-pentenyl, n-1-decenyl, and n-1-eicosenyl.

[0020] The alkynyl group may be linear, branched, or cyclic. Specific examples thereof include an ethynyl group, an n-1-propynyl group, an n-2-propynyl group, an n-1-butynyl group, an n-2-butynyl group, an n-3-butynyl group, a 1-methyl-2-propynyl group, an n-1-pentynyl group, an n-2-pentynyl group, an n-3-pentynyl group, an n-4-pentynyl group, a 1-methyl-n-butynyl group, a 2-methyl-n-butynyl group, a 3-methyl-n-butynyl group, a 1,1-dimethyl-n-propynyl group, an n-1-hexynyl group, an n-1-decynyl group, an n-1-pentadecinyl group, and an n-1-eicosynyl group.

[0021] Specific examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group.

[0022] Specific examples of the heteroaryl group include a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, a 3-furanyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 3-isoxazolyl group, a 4-isoxazolyl group, a 5-isoxazolyl group, a 2-thiazolyl group, a 4-thiazolyl group, a 5-thiazolyl group, a 3-isothiazolyl group, a 4-isothiazolyl group, a 5-isothiazolyl group, a 2-imidazolyl group, a 4-imidazolyl group, a 2-pyridyl group, a 3-pyridyl group, and a 4-pyridyl group.

[0023] Of these, R 1 ~R 6 is 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.

[0024] X 1 As the group, a group represented by the following formula (4') is most preferable. [ka] (In the formula, the dashed lines represent bonds.)

[0025] In formula (1), Y 1 represents a divalent aromatic group having 6 to 14 carbon atoms. 2 represents a group represented by the following formula (3). [ka]

[0026] In 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 the same as those mentioned above. Z 1 As the alkyl group, -O- and -NH- are preferable.

[0027] In formula (3), Ar 1 and Ar 2 each independently represents a divalent aromatic group having 6 to 14 carbon atoms.

[0028] Y 1 , Ar 1 and Ar 2 Examples of the divalent aromatic group represented by the formula (I) include a phenylene group, a naphthylene group, an anthracenediyl group, a phenanthrenediyl group, and a biphenyldiyl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent.

[0029] Y 1 is preferably a group represented by the following formula (5), 2 is preferably a group represented by the following formula (6). [ka]

[0030] In the formula, Z 1 is the same as above. 7 ~R 18 are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom. A dashed line represents a bond. Examples of the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group include those similar to those described above.

[0031] R 7 ~R 18 is 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, still more preferably a hydrogen atom, a methyl group, or a halogen atom, and most preferably a hydrogen atom.

[0032] Y 2 As the group represented by the following formula (7), (8) or (9) is most preferable. [ka] (In the formula, the broken line represents a bond.)

[0033] In formulas (1) and (2), n and m represent positive numbers satisfying 0 < n < 100, 0 < m < 100, and 0 < n + m ≤ 100. From the viewpoints of solubility and heat resistance, n and m are preferably positive numbers satisfying 5 ≤ n ≤ 25, 75 ≤ m ≤ 95, and 80 ≤ n + m ≤ 100, more preferably positive numbers satisfying 10 ≤ n ≤ 25, 75 ≤ m ≤ 90, and 85 ≤ n + m ≤ 100, and even more preferably positive numbers satisfying 20 ≤ n ≤ 25, 75 ≤ m ≤ 80, and 95 ≤ n + m ≤ 100.

[0034] The polyhydroxyamide may contain units other than the unit represented by formula (1) and the unit represented by formula (2) (hereinafter also referred to as other units).

[0035] 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 the average molecular weight obtained by conversion to standard polystyrene by gel permeation chromatography (GPC) analysis.

[0036] [Method for producing polyhydroxyamide] The polyhydroxyamide can be produced by subjecting 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) to condensation polymerization in a solvent, optionally in the presence of a base. [Chemical formula] (In the formula, X 1 , Y 1 and Y 2 are the same as above. Hal represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom.)

[0037] In this case, the amount of the dicarboxylic acid derivative represented by formula (13) used is preferably 0.05 to 0.25 mol, more preferably 0.10 to 0.25 mol, and even more preferably 0.20 to 0.25 mol, relative to 1 mol of the diamine compound represented by formula (12). The amount of the dicarboxylic acid derivative represented by formula (14) used is preferably 0.75 to 0.95 mol, more preferably 0.75 to 0.90 mol, and even more preferably 0.75 to 0.80 mol, relative to 1 mol of the diamine compound represented by formula (12).

[0038] 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, and 3-butoxy-N,N-dimethylpropanamide.

[0039] Examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium hydrogencarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, 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, etc. 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.

[0040] The reaction temperature may be appropriately set within the range from the melting point of the solvent used to the boiling point of the solvent, and is usually about -20 to 100°C, and preferably about -10 to 100°C. The polymerization reaction time is usually about 1 to 48 hours, and preferably about 1 to 24 hours. After the reaction is completed, post-treatment is carried out according to a standard method, and purification such as reprecipitation is carried out as necessary to obtain the target product.

[0041] [(B) Organic solvent] The organic solvent of component (B) is not particularly limited as long as it can dissolve the polyhydroxyamide. However, in consideration of reproducibly obtaining a polybenzoxazole resin film with high flatness, it is preferable to use an organic solvent containing at least one selected from the group consisting of amides represented by the following formula (S1), amides represented by the following formula (S2), and amides represented by the following formula (S3). [ka]

[0042] In the formula, R 21 and R 22 R each independently represents an alkyl group having 1 to 10 carbon atoms. 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 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, a sec-butyl group, and a tert-butyl group.

[0043] In formula (S1), a represents a natural number, preferably a natural number of 1 to 3, and more preferably 1 or 2.

[0044] Examples of the organic solvent represented by 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, and 3-tert-butoxy-N,N-dimethylpropylamide.

[0045] Examples of the organic solvent represented by formula (S2) include N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, and N-butyl-2-pyrrolidone.

[0046] Examples of the organic solvent represented by formula (S3) include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, and N,N-dimethylisobutyramide.

[0047] In addition, even if the solvent does not dissolve the polyhydroxyamide alone, it can be added 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, 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, and isoamyl lactate.

[0048] The concentration of polyhydroxyamide in the polyhydroxyamide composition is appropriately set taking into consideration the thickness of the resin film to be produced, the viscosity of the composition, etc., but is usually about 1 to 30 mass %, preferably about 1 to 20 mass %.

[0049] [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 the composition to evaporate the solvent and ring-close the polyhydroxyamide.

[0050] Examples of the substrate include glass, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose, ABS, AS, norbornene-based resin, etc.), metals (silicon wafer, etc.), glass substrates with vapor-deposited films such as SiN and SiO films, wood, paper, slate, etc., and from the viewpoint of productivity, glass, metals (silicon wafer, etc.) are particularly preferred. The substrate surface may be composed of a single material or two or more materials.

[0051] The method for applying the polyhydroxyamide composition is not particularly limited, but examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0052] The heating temperature when evaporating the organic solvent is preferably 50 to 200° C., more preferably 50 to 150° C. The heating time at this time is preferably 5 minutes to 5 hours, more preferably 5 minutes to 3 hours.

[0053] At this time, the heating temperature for ring closure is appropriately determined usually within the range of 50 to 550°C, but is preferably 200°C or higher, and preferably 500°C or lower. By setting the heating temperature in this manner, it becomes possible to prevent the obtained film from becoming brittle and to allow the oxazolization reaction to proceed sufficiently. The heating time cannot be generally specified because it varies depending on the heating temperature, but is usually 5 minutes to 5 hours. In addition, the ring closure rate may be in the range of 50 to 100%.

[0054] A preferred example of the heating mode is a method in which the material is heated at 50 to 100° C. for 5 minutes to 2 hours, and then the heating temperature is gradually increased to a temperature of more than 375° C. to 450° C. for 30 minutes to 4 hours. In particular, it is preferred to heat the material at 50 to 100° C. for 5 minutes to 2 hours, then at more than 100° C. to 375° C. for 5 minutes to 2 hours, and finally at more than 375° C. to 450° C. for 30 minutes to 4 hours.

[0055] The thickness of the resin film is not particularly limited, but when used as a substrate for an electronic device described later, it is usually about 1 to 100 μm, and from the viewpoint of sufficient self-supporting property and flexibility, it is preferably about 5 to 75 μm, and more preferably about 5 to 50 μm.

[0056] After the resin film is formed, it can be peeled off from the substrate and collected by immersion in water, a laser lift-off method using ultraviolet light with a wavelength of 308 nm, or the like.

[0057] 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 8 ppm / °C or lower at 50 to 400°C.

[0058] [Electronic Devices] The electronic device of the present invention includes the polybenzoxazole resin film as a substrate. Examples of the electronic device include an organic electroluminescence (EL) element, a liquid crystal display, an organic electroluminescence (EL) display, an optical semiconductor (LED) element, an electronic paper, a solid-state imaging element, an organic thin-film solar cell, a dye-sensitized solar cell, an organic thin-film transistor (TFT), a 3D display, and a touch panel.

[0059] An example of a method for producing an electronic device of the present invention will be described. By the above-mentioned method, the polyhydroxyamide composition is applied onto 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 with the circuit formed thereon is peeled off from the substrate to separate the resin film with the circuit formed thereon from the substrate, thereby producing an electronic device. EXAMPLES

[0060] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The compounds used in the following examples and the methods for measuring the weight average molecular weight and molecular weight distribution are as follows.

[0061] 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

[0062] [Measurement of weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)] The Mw and Mw / Mn of the polymer were measured using a GPC device manufactured by JASCO Corporation (column: Shodex (registered trademark) columns KF803L and KF805L manufactured by Showa Denko K.K., elution solvent: dimethylformamide, flow rate: 1.0 mL / min, column temperature: 50° C., Mw: value calculated in terms of standard polystyrene).

[0063] [1] Polymer synthesis [Example 1] Synthesis of polyhydroxyamide P1 1.052g (4.87mmol) of HAB was dissolved in 27.6g of NMP, and 0.963g (12.18mmol) of pyridine was added, followed by 1.149g (3.90mmol) of DEDC and 0.198g (0.97mmol) of TPC, and the mixture was stirred at room temperature for 24 hours. The resulting solution was then poured into 500mL of pure water. The resulting precipitate was filtered and dried under reduced pressure at 70°C for 24 hours to obtain the desired polyhydroxyamide P1. The Mw of polyhydroxyamide P1 measured by GPC was 60,300, and the Mw / Mn was 2.8.

[0064] [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 used, the amount of NMP used, Mw, and Mw / Mn.

[0065] [2] Evaluation of the solubility of polyhydroxyamide 1 g of the prepared polyhydroxyamide was added to 20 g of NMP, and the mixture was stirred at room temperature for 48 hours to dissolve again. The results are shown in Table 1. The evaluation criteria for solubility are as follows. ◯: Dissolves during polymerization and dissolves again after purification. △: Dissolves during polymerization, but does not dissolve again after purification. ×: Precipitation occurs during polymerization.

[0066] [Table 1]

[0067] [2] Preparation and evaluation of polybenzoxazole resin film [Thickness before curing / Removal method] 1 g of the polyhydroxyamides produced in Examples 1 and 2 and Comparative Example 5 was dissolved in 20 mL of NMP to prepare polyhydroxyamide compositions. Each of the compositions obtained was applied to a 100 mm x 100 mm glass substrate using a bar coater, and baked on a hot plate at 80 ° C. for 30 minutes. After that, it was heated at 140 ° C. for 30 minutes, the heating temperature was raised to 210 ° C. (10 ° C. / min, the same below), 210 ° C. for 30 minutes, the heating temperature was raised to 300 ° C., 300 ° C. for 30 minutes, the heating temperature was raised to 400 ° C., and 400 ° C. for 60 minutes. During the temperature increase, the film-coated substrate was not taken out of the oven, but was heated in the oven. The film thickness of the obtained coating film was measured with a contact film thickness measuring instrument (Dektak 3ST manufactured by ULVAC Co., Ltd.). The film thickness measurement results are shown in Table 2. After that, the glass substrate was left to stand in pure water at 70 ° C. in a 1 L beaker, and the film was peeled off.

[0068] [Linear expansion coefficient] A 20 mm × 5 mm strip was cut from the obtained film, and the linear expansion coefficient was measured by heating from 50°C to 400°C at a rate of 10°C / min using a TMA-4000SA (manufactured by Bruker AXS Co., Ltd.). The results are shown in Table 2.

[0069] [5% weight loss temperature] A 20 mm x 3 mm strip was cut from the obtained film, and the weight loss was measured from 50°C to 600°C using a TGA-DTA-2000SR (manufactured by Bruker AXS Co., Ltd.) to confirm the 5% weight loss temperature. The results are shown in Table 2. In addition, when there was no 5% weight loss at 600°C, it was recorded as 600°C<.

[0070] [Self-supporting] The prepared film was peeled off and then bent 90° in all directions. If there was no particular change, the film was deemed to have self-supporting properties. The results are shown in Table 2. The evaluation criteria for the self-supporting property are as follows. ○: Self-supporting. Will not break even when bent 90 degrees. △: Self-supporting, but breaks when bent ×: No self-supporting property ××: Disassembled on the board

[0071] [Table 2]

Claims

1. A polyhydroxyamide composition for use in producing a substrate for an electronic device, comprising: (A) a polyhydroxyamide containing a unit represented by the following formula (1) and a unit represented by the following formula (2); and (B) an organic solvent. 【Chemistry 1】 [In the formula, 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 satisfy 5 mol %≦n≦25 mol %, 75 mol %≦m≦95 mol %, and n+m=100 mol %. 【Chemistry 2】 (In the formula, Z 1 represents -O-; Ar 1 and Ar 2 each independently represents a divalent aromatic group having 6 to 14 carbon atoms; the dashed line represents a bond.

2. X 1 The polyhydroxyamide composition for use in producing a substrate for an electronic device according to claim 1, wherein is a group represented by the following formula (4): 【Chemistry 3】 (In the formula, R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom; a dashed line represents a bond.

3. X 1 The polyhydroxyamide composition for use in producing a substrate for an electronic device according to claim 2, wherein is a group represented by the following formula (4'): 【Chemistry 4】 (In the formula, the dashed lines represent bonds.)

4. Y 1 is a group represented by the following formula (5), and Y 2 The polyhydroxyamide composition for use in producing a substrate for an electronic device according to any one of claims 1 to 3, wherein 【Chemistry 5】 (In the formula, Z 1 is the same as above; R 7 ~R 18 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom; a dashed line represents a bond.

5. R 7 ~R 18 The polyhydroxyamide composition for use in producing a substrate for an electronic device according to claim 4, wherein is a hydrogen atom.

6. Y 2 The polyhydroxyamide composition for use in producing a substrate for an electronic device according to any one of claims 1 to 5, wherein is a group represented by the following formula (7), (8) or (9): 【Chemistry 6】 (In the formula, the dashed lines represent bonds.)

7. The polyhydroxyamide composition for electronic device substrates according to any one of claims 1 to 6, wherein the organic solvent (B) contains at least one selected from the group consisting of amides represented by the following formula (S1), amides represented by the following formula (S2), and amides represented by the following formula (S3): 【Chemistry 7】 (In the formula, R 21 and R 22 R each independently represents an alkyl group having 1 to 10 carbon atoms. 23 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a represents a natural number.

8. A method for producing a polybenzoxazole resin film for use in a substrate for an electronic device, comprising the steps of: applying the polyhydroxyamide composition for use in producing a substrate for an electronic device according to any one of claims 1 to 7 onto a substrate; and heating to evaporate the solvent and ring-close the polyhydroxyamide.

9. A polybenzoxazole resin film for use as a substrate for electronic devices, obtained from the polyhydroxyamide composition according to any one of claims 1 to 7.

10. 10. The polybenzoxazole resin film for electronic device substrates according to claim 9, which has a 5% weight loss temperature of 600° C. or higher and a linear expansion coefficient from 50 to 400° C. of 8 ppm / ° C. or lower.

11. An electronic device comprising the polybenzoxazole resin film for electronic device substrates according to claim 9 or 10 as a substrate.

12. A polyhydroxyamide comprising a unit represented by the following formula (10) and a unit represented by the following formula (11): 【Chemistry 8】 [In the formula, 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 satisfy 5 mol %≦n≦25 mol %, 75 mol %≦m≦95 mol %, and n+m=100 mol %. 【Chemistry 9】 (In the formula, Z 1 represents -O-; Ar 1 and Ar 2 each independently represents a divalent aromatic group having 6 to 14 carbon atoms; the dashed line represents a bond.

13. X 1 The polyhydroxyamide according to claim 12, wherein is a group represented by the following formula (4): 【Chemistry 10】 (In the formula, R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom; a dashed line represents a bond.

14. X 1 The polyhydroxyamide according to claim 13, wherein is a group represented by the following formula (4'): 【Chemistry 11】 (In the formula, the dashed lines represent bonds.)

15. Y 1 is a group represented by the following formula (5), and Y 2 The polyhydroxyamide according to any one of claims 12 to 14, wherein 【Chemistry 12】 (In the formula, Z 1 is the same as above; R 7 ~R 18 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom; a dashed line represents a bond.

16. R 7 ~R 18 The polyhydroxyamide according to claim 15, wherein is a hydrogen atom.

17. Y 2 The polyhydroxyamide according to any one of claims 12 to 16, wherein is a group represented by the following formula (7), (8) or (9): 【Chemistry 13】 (In the formula, the dashed lines represent bonds.)

18. A method for producing a polyhydroxyamide, comprising condensation polymerizing 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 per 1 mol of the diamine compound, and a dicarboxylic acid derivative represented by the following formula (14) in an amount of 0.75 to 0.95 mol per 1 mol of the diamine compound, in a solvent, in the presence of a catalyst. 【Chemistry 14】 [In the formula, 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). 【Chemistry 15】 (In the formula, Z 1 represents -O-; Ar 1 and Ar 2 each independently represents a divalent aromatic group having 6 to 14 carbon atoms; the dashed line represents a bond.

19. X 1 The method for producing a polyhydroxyamide according to claim 18, wherein is a group represented by the following formula (4): 【Chemistry 16】 (In the formula, R 1 ~R 6 each independently represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom; a dashed line represents a bond.

20. X 1 The method for producing a polyhydroxyamide according to claim 19, wherein is a group represented by the following formula (4'): 【Chemistry 17】 (In the formula, the dashed lines represent bonds.)

21. Y 1 is a group represented by the following formula (5), and Y 2 The method for producing a polyhydroxyamide according to any one of claims 18 to 20, wherein 【Chemistry 18】 (In the formula, Z 1 is the same as above; R 7 ~R 18 each independently represents a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, or 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, each of which may be substituted with a halogen atom; a dashed line represents a bond.

22. R 7 ~R 18 The method for producing a polyhydroxyamide according to claim 21, wherein is a hydrogen atom.

23. Y 2 The method for producing a polyhydroxyamide according to any one of claims 18 to 22, wherein is a group represented by the following formula (7), (8) or (9): 【Chemistry 19】 (In the formula, the dashed lines represent bonds.)

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