JP2019172970A - Resin composition for substrate of display device or light-receiving device, substrate of display device or light-receiving device using the same, display device, light-receiving device, and method for manufacturing display device or light-receiving device - Google Patents

Abstract

（Ｘ：炭素数２以上の４価のテトラカルボン酸残基、Ｙ：炭素数２以上の２価のジアミン残基。ただし、樹脂中の全てのＸおよびＹのうちの１モル％以上は、炭素数４〜８の脂環式炭化水素の少なくとも４つ以上の水素原子が炭素数４〜１２の炭化水素基で置換された構造を有する、４価のテトラカルボン酸残基および／または２価のジアミン残基。）
【選択図】なしDisclosed is a resin composition for a substrate of a display device or a light receiving device, which can generate less stress when deposited on a support and can reduce irradiation energy during laser lift-off.
A resin composition comprising a resin whose main component is a repeating unit represented by formula (1) or a precursor thereof and used as a substrate of a display device or a light receiving device.

(X: a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms, Y: a divalent diamine residue having 2 or more carbon atoms. However, 1 mol% or more of all X and Y in the resin is A tetravalent tetracarboxylic acid residue and / or a divalent structure having a structure in which at least 4 or more hydrogen atoms of an alicyclic hydrocarbon having 4 to 8 carbon atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms Diamine residue.)
[Selection figure] None

Description

  The present invention relates to a resin composition for a substrate of a display device or a light receiving device, and a substrate for a display device or a light receiving device using the same, a display device, a light receiving device, a display device, or a method for manufacturing the light receiving device.

  Polyimide is used as a material for various electronic devices due to its excellent electrical insulation, heat resistance, and mechanical properties. Recently, by using a heat-resistant resin film on the substrate of organic EL displays, electronic paper, liquid crystal displays, micro LEDs, and other light-receiving devices such as solar cells, flexible display devices and light-receiving devices that are resistant to impact. Can be manufactured.

  When using a polyimide film as a substrate for a display device or a light-receiving device, first, a solution containing a polyamic acid resin, which is a polyimide resin or a polyimide resin precursor (hereinafter referred to as “polyimide varnish”), is applied to a support such as a glass substrate. To do. Various elements are formed on a polyimide film obtained by heating and curing this. Finally, a display device and a light receiving device using the polyimide film as a substrate can be obtained by irradiating a laser to peel off both at the interface between the support and the polyimide film (hereinafter referred to as laser lift-off).

  By the way, when the thermal linear expansion coefficient of the glass substrate which is a support body and the thermal linear expansion coefficient of a polyimide film are mismatched, a stress generate | occur | produces between a glass substrate and a polyimide film. This stress warps the glass substrate, and there is a problem that the process passability is lowered. In order to solve this, a polyimide varnish containing a polyamic acid resin into which a polysiloxane structure is introduced has been developed for the purpose of relaxing the generated stress with a polyimide film (see, for example, Patent Documents 1 and 2).

International Publication No. 2014/098235 International Publication No. 2014/148441

  However, the polyimide film obtained from the polyimide varnish described in Patent Documents 1 and 2 has a problem that the irradiation energy required for laser lift-off is high when peeling from the glass substrate. An excimer laser with a wavelength of 308 nm is usually used for laser lift-off. However, the excimer laser has a higher running cost than the solid laser, and the reduction of laser irradiation energy has been a problem.

  An object of this invention is to solve the subject of the reduction of the stress of a film when using a polyimide film as a board | substrate of a display device or a light receiving device, and the reduction of the irradiation energy at the time of a laser lift-off.

  The present invention is a resin composition containing a resin whose main component is a repeating unit represented by the chemical formula (1) or (2) and used as a substrate of a display device or a light receiving device.

(In the chemical formulas (1) and (2), X represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms, and Y represents a divalent diamine residue having 2 or more carbon atoms. However, in the resin, 1 mol% or more of all X and Y has a structure in which at least 4 or more hydrogen atoms of an alicyclic hydrocarbon having 4 to 8 carbon atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms. A tetravalent tetracarboxylic acid residue and / or a divalent diamine residue, wherein R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms; Represents an alkylsilyl group, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion.)

  According to the present invention, it is possible to obtain a resin composition that generates less stress and can reduce irradiation energy necessary for laser lift-off. This resin composition is suitably used as a substrate for a display device or a light receiving device.

  Hereinafter, a resin composition according to the present invention, a manufacturing method of a display device or a light receiving device using the resin composition, a substrate, and a preferred embodiment of a display device or a light receiving device using the substrate will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various modifications according to the purpose and application.

<Resin composition>
The resin composition according to the present invention is a resin composition for a substrate of a display device or a light-receiving device, comprising a resin whose main component is a repeating unit represented by the chemical formula (1) or (2).

In chemical formulas (1) and (2), X represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms, and Y represents a divalent diamine residue having 2 or more carbon atoms. However, 1 mol% or more of all X and Y in the resin is substituted with at least 4 or more hydrogen atoms of the alicyclic hydrocarbon having 4 to 8 carbon atoms by a hydrocarbon group having 4 to 12 carbon atoms. A tetravalent tetracarboxylic acid residue and / or a divalent diamine residue having the above structure is shown. R ¹ and R ² each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 10 carbon atoms, an alkali metal ion, an ammonium ion, an imidazolium ion, or a pyridinium ion.

(resin)
Chemical formula (1) shows the chemical structure of polyimide. Chemical formula (2) shows the chemical structure of the polyamic acid. The polyamic acid is obtained by reacting a tetracarboxylic acid and a diamine compound as described later. Furthermore, polyamic acid can be converted to polyimide, which is a heat-resistant resin, by heating or chemical treatment.

  In the chemical formulas (1) and (2), X may contain a hydrogen atom and a carbon atom as essential components, and may contain one or more atoms selected from the group consisting of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen. A good tetravalent organic group having 2 to 80 carbon atoms is preferable, and a tetravalent hydrocarbon group having 2 to 80 carbon atoms is more preferable. Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is preferably independently in a range of 20 or less, more preferably in a range of 10 or less.

  There is no restriction | limiting in particular as tetracarboxylic acid which gives X, A well-known thing can be used. Examples include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, bis (3,4-dicarboxyphenyl) sulfone, bis (3 , 4-dicarboxyphenyl) ether, cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and International Publication No. 2017/099183. And the tetracarboxylic acids described.

  These tetracarboxylic acids can be used as they are or in the form of acid anhydrides, active esters, and active amides. Of these, acid anhydrides are preferably used because no by-products are produced during polymerization. Two or more of these may be used.

  In addition, in order to improve the coating property on the support, the resistance to oxygen plasma used for cleaning, and UV ozone treatment, silicon-containing tetra- amides such as dimethylsilane diphthalic acid and 1,3-bis (phthalic acid) tetramethyldisiloxane are used. Carboxylic acid may be used. When using these silicon-containing tetracarboxylic acids, it is preferable to use 1-30 mol% of the total tetracarboxylic acids.

In the tetracarboxylic acid exemplified above, a part of the hydrogen atoms contained in the tetracarboxylic acid residue is a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, or a carbon number of 1 such as a trifluoromethyl group. Optionally substituted with 10 to 10 fluoroalkyl groups, such as F, Cl, Br, and I. Furthermore, when substituted with an acidic group such as OH, COOH, SO ₃ H, CONH ₂ , or SO ₂ NH ₂ , the solubility of the resin in an aqueous alkali solution is improved, so that it is used as a photosensitive resin composition described later. Preferred in some cases.

  In chemical formulas (1) and (2), Y may contain a hydrogen atom and a carbon atom as essential components, and may contain one or more atoms selected from the group consisting of boron, oxygen, sulfur, nitrogen, phosphorus, silicon, and halogen. A divalent organic group having 2 to 80 carbon atoms is preferable, and a divalent hydrocarbon group having 2 to 80 carbon atoms is more preferable. Each atom of boron, oxygen, sulfur, nitrogen, phosphorus, silicon and halogen is preferably independently in a range of 20 or less, more preferably in a range of 10 or less.

  There is no restriction | limiting in particular as diamine which gives Y, A well-known thing can be used. Examples include m-phenylenediamine, p-phenylenediamine, 4,4′-diaminobenzanilide, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 2,2′-dimethyl-4,4′-. Diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, bis (4-aminophenoxyphenyl) sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3- Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, ethylenediamine, propylenediamine, butanediamine, cyclohexanediamine, 4, 4'-methylenebis (cyclohexylamine) and international Such diamines described in JP Hirakidai 2017/099183 and the like.

  These diamines can be used as they are or in the state of the corresponding trimethylsilylated diamine. Two or more of these may be used.

  In addition, in order to improve the coating property to the support, the resistance to oxygen plasma used for cleaning and UV ozone treatment, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4 -Anilino) silicon-containing diamines such as tetramethyldisiloxane may be used. When using these silicon-containing diamine compounds, it is preferable to use 1-30 mol% of the whole diamine compounds.

In the diamine compound exemplified above, a part of hydrogen atoms contained in the diamine compound is a hydrocarbon group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, or a fluoroalkyl having 1 to 10 carbon atoms such as a trifluoromethyl group. It may be substituted with a group such as F, Cl, Br, or I. Furthermore, when substituted with an acidic group such as OH, COOH, SO ₃ H, CONH ₂ , or SO ₂ NH ₂ , the solubility of the resin in an aqueous alkali solution is improved, so that it is used as a photosensitive resin composition described later. Preferred in some cases.

  The resin having a repeating unit represented by the chemical formula (1) or (2) as a main component means that the repeating number of the repeating unit occupies 50% or more of all the repeating numbers. In this resin, the repeating unit preferably occupies 80% or more of the total repeating units, and more preferably 90% or more. If it is 50% or more, heat resistance necessary for use as a substrate of a display device or a light receiving device is secured.

  1 mol% or more of all X and Y in the resin is substituted with at least 4 or more hydrogen atoms of an alicyclic hydrocarbon having 4 to 8 carbon atoms by a hydrocarbon group having 4 to 12 carbon atoms. A tetravalent tetracarboxylic acid residue and / or a divalent diamine residue having the above structure. The proportion of such tetracarboxylic acid residues and / or diamine residues is preferably 3 mol% or more, more preferably 5 mol% or more, of all X and Y in the resin. Moreover, less than 50 mol% is preferable and less than 30 mol% is more preferable. When the ratio is 1 mol% or more, the above-described stress can be reduced and laser lift-off energy can be reduced. If it is less than 50 mol%, more preferably less than 30 mol%, the heat resistance necessary for use as a substrate of a display device or a light receiving device can be maintained.

  Moreover, as for resin which has as a main component the repeating unit represented by Chemical formula (1) or (2), 1 mol% or more of all the Y in resin is C4-C8 alicyclic hydrocarbon It is preferable that at least 4 or more hydrogen atoms are divalent diamine residues having a structure substituted with a hydrocarbon group having 4 to 12 carbon atoms. The proportion of such diamine residues is preferably 3 mol% or more of all Y in the resin, and more preferably 5 mol% or more. Moreover, less than 50 mol% is preferable and less than 30 mol% is more preferable. When the ratio is 1 mol% or more, the above-described stress can be reduced and laser lift-off energy can be reduced. If it is less than 50 mol%, more preferably less than 30 mol%, the heat resistance necessary for use as a substrate of a display device or a light receiving device can be maintained.

  Among such diamines that give Y, a diamine represented by the chemical formula (5) is preferable, a diamine represented by any one of the chemical formulas (6) to (9) is more preferable, and a chemical formula is most preferable. It is a diamine represented by (6). Chemical formulas (6) to (8) are hydrogenated products of chemical formula (9), and when the diamine represented by chemical formula (6) in which all unsaturated bonds are hydrogenated is used, in the laser lift-off described later The lowest peel energy. Examples of commercially available products of these diamines include preamine 1073, preamine 1074, preamine 1075 (manufactured by Croda Informational plc), versamin 551, and versamin 552 (manufactured by Cognis).

  In chemical formula (5), m represents an integer of 4 to 8. m pieces of W each independently represent any of the structural units represented by the chemical formulas (5a) to (5d). Z in the chemical formula (5b) and U in the chemical formula (5c) represent a hydrogen atom or an amino group. n and k each represent an integer of 3 to 11.

  The resin whose main component is the repeating unit represented by the chemical formula (1) or (2) may have a terminal sealed with a terminal blocking agent. The molecular weight of a polyimide precursor can be adjusted to a preferable range by making terminal blocker react.

  When the terminal monomer is a diamine compound, dicarboxylic acid anhydride, monocarboxylic acid, monocarboxylic acid chloride compound, monocarboxylic acid active ester compound, dicarbonic acid dialkyl ester, etc. are terminated to seal the amino group. It can be used as a sealant.

  When the terminal monomer is an acid dianhydride, a monoamine, monoalcohol or the like can be used as the terminal blocking agent in order to seal the acid anhydride group.

  The weight average molecular weight of the resin having the repeating unit represented by the chemical formula (1) or (2) as a main component is preferably 200,000 or less, more preferably 150,000 in terms of polystyrene using gel permeation chromatography. Hereinafter, it is more preferable that it is 100,000 or less. If it is this range, even if it is a high concentration resin composition, it can suppress more that a viscosity increases. The weight average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, and further preferably 30,000 or more. If a weight average molecular weight is 30,000 or more, the viscosity when it is set as a resin composition will not fall too much, and more favorable applicability | paintability can be maintained.

  The number of repetitions of chemical formulas (1) and (2) may be in a range satisfying the above-mentioned weight average molecular weight. Preferably it is 5 or more, More preferably, it is 10 or more. Moreover, it is preferably 1000 or less, more preferably 500 or less.

(solvent)
The resin composition in the present invention may contain a solvent. When it contains a solvent, it can be used as a polyimide varnish. By coating such a polyimide varnish on various supports, a coating film containing a resin whose main component is the repeating unit represented by the chemical formula (1) or (2) can be formed on the support. Furthermore, the polyimide film which can be used as a board | substrate of a display device or a light receiving device is obtained by heat-processing and hardening the obtained coating film.

  There is no restriction | limiting in particular as a solvent, A well-known thing can be used. Examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, 1,1,3,3-tetramethylurea, dimethylsulfoxide, Use sulfolane, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, water, or the solvent described in International Publication No. 2017/099183, alone or in combination. It can be.

  The content of the solvent is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, with respect to 100 parts by mass of the resin whose main component is the repeating unit represented by the chemical formula (1) or (2). , Preferably it is 2000 mass parts or less, More preferably, it is 1500 mass parts or less. If it is the range which satisfy | fills this condition, it will become a viscosity suitable for application | coating and the film thickness after application | coating can be adjusted easily.

  The viscosity of the resin composition in the present invention is preferably 20 to 10,000 mPa · s, more preferably 50 to 8,000 mPa · s. If the viscosity is less than 20 mPa · s, a resin film having a sufficient thickness cannot be obtained, and if it is greater than 10,000 mPa · s, it becomes difficult to apply the resin composition.

(Additive)
The resin composition according to the present invention includes (a) a photoacid generator, (b) heat, in addition to a resin mainly composed of a repeating unit represented by the chemical formula (1) or (2) (hereinafter referred to as a resin). It contains at least one additive selected from a crosslinking agent, (c) a thermal acid generator, (d) a compound containing a phenolic hydroxyl group, (e) an adhesion improver, (f) inorganic particles, and (g) a surfactant. But you can. Specific examples of these additives include those described in International Publication No. 2017/099183.

(A) Photoacid generator The resin composition of this invention can be made into the photosensitive resin composition by containing a photoacid generator. By containing the photoacid generator, an acid is generated in the light irradiation part, the solubility of the light irradiation part in the alkaline aqueous solution is increased, and a positive relief pattern in which the light irradiation part is dissolved can be obtained. In addition, by containing a photoacid generator and an epoxy compound or a thermal cross-linking agent described later, the acid generated in the light irradiation part accelerates the cross-linking reaction of the epoxy compound or the heat cross-linking agent, and the light irradiation part becomes insoluble. The relief pattern can be obtained.

  Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Two or more of these may be contained, and a highly sensitive photosensitive resin composition can be obtained.

(B) Thermal crosslinking agent The resin composition of this invention can improve the chemical resistance and hardness of the resin film obtained by heating by containing a thermal crosslinking agent. The content of the thermal crosslinking agent is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin. If content of a thermal crosslinking agent is 10 mass parts or more and 100 mass parts or less, the intensity | strength of the obtained heat resistant resin film is high, and it is excellent also in the storage stability of a resin composition.

(C) Thermal acid generator The resin composition of the present invention may further contain a thermal acid generator. The thermal acid generator generates an acid by heating after development, which will be described later, and accelerates the crosslinking reaction between the heat-resistant resin or its precursor and the thermal crosslinking agent, and also accelerates the curing reaction. For this reason, the chemical resistance of the resulting heat-resistant resin film is improved, and film loss can be reduced. The acid generated from the thermal acid generator is preferably a strong acid. For example, arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, and alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid are preferable. The content of the thermal acid generator is preferably 0.5 parts by mass or more and preferably 10 parts by mass or less with respect to 100 parts by mass of the resin from the viewpoint of further promoting the crosslinking reaction.

(D) Compound containing phenolic hydroxyl group If necessary, a compound containing a phenolic hydroxyl group may be contained for the purpose of supplementing the alkali developability of the photosensitive resin composition. By containing a compound containing a phenolic hydroxyl group, the resulting photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Therefore, development can be easily performed in a short time. Therefore, the sensitivity is easily improved. The content of such a compound containing a phenolic hydroxyl group is preferably 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin.

(E) Adhesion improving agent The varnish in the present invention may contain an adhesion improving agent. By containing an adhesion improving agent, the adhesion to a base substrate such as a silicon wafer, ITO, SiO ₂ or silicon nitride can be improved when developing a photosensitive resin film. In addition, by improving the adhesion between the heat-resistant resin film and the underlying base material, resistance to oxygen plasma and UV ozone treatment used for cleaning can be increased. In addition, it is possible to suppress a film floating phenomenon in which the resin film floats from the substrate in a vacuum process during firing or display manufacturing. The content of the adhesion improving agent is preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the resin.

(F) Inorganic particles
The resin composition of the present invention can contain inorganic particles for the purpose of improving heat resistance. Inorganic particles used for such purposes include inorganic metal particles such as platinum, gold, palladium, silver, copper, nickel, zinc, aluminum, iron, cobalt, rhodium, ruthenium, tin, lead, bismuth, tungsten, and silicon oxide. (Silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, tungsten oxide, zirconium oxide, calcium carbonate, barium sulfate, and other metal oxide inorganic particles. The shape of the inorganic particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a flat shape, a lot shape, and a fiber shape. In order to suppress an increase in the surface roughness of the heat resistant resin film containing inorganic particles, the average particle size of the inorganic particles is preferably 1 nm to 100 nm, and more preferably 1 nm to 50 nm. More preferably, it is 1 nm or more and 30 nm or less.

  The content of the inorganic particles is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass with respect to 100 parts by mass of the resin. It is not more than part by mass, more preferably not more than 50 parts by mass. When the content of the inorganic particles is 3 parts by mass or more, the heat resistance is sufficiently improved, and when the content is 100 parts by mass or less, the toughness of the heat-resistant resin film is hardly lowered.

(G) Surfactant The resin composition of the present invention may contain a surfactant in order to improve coatability. As surfactants, “Florard” (registered trademark) manufactured by Sumitomo 3M Co., Ltd., “Megafac” (registered trademark) manufactured by DIC Corporation, “sulfuron” (registered trademark) manufactured by Asahi Glass Co., Ltd., etc. Fluorosurfactant, Shin-Etsu Chemical Co., Ltd. KP341, Chisso Co., Ltd. DBE, Kyoeisha Chemical Co., Ltd. “Polyflow” (registered trademark), “Granol” (registered trademark), Examples thereof include organic siloxane surfactants such as BYK manufactured by Chemie Corp. and acrylic polymer surfactants such as polyflow manufactured by Kyoeisha Chemical Co., Ltd. It is preferable to contain 0.01-10 mass parts of surfactant with respect to 100 mass parts of resin.

<Method for producing resin composition>
The resin of the present invention is dissolved by dissolving the above resin and, if necessary, a photoacid generator, a thermal crosslinking agent, a thermal acid generator, a compound containing a phenolic hydroxyl group, an adhesion improver, inorganic particles, and a surfactant in a solvent. The varnish which is one of the embodiments of the composition can be obtained. Examples of the dissolution method include stirring and heating. When the photoacid generator is included, the heating temperature is preferably set in a range that does not impair the performance as the photosensitive resin composition, and is usually room temperature to 80 ° C. In addition, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. Moreover, about the component which is easy to generate | occur | produce a bubble at the time of stirring dissolution, such as surfactant, the melt | dissolution failure of the other component by generation | occurrence | production of a bubble can be prevented by adding last after melt | dissolving another component.

  The resin can be polymerized by a known method. For example, polyamic acid is obtained by polymerizing tetracarboxylic acid or corresponding acid dianhydride, active ester, active amide or the like as an acid component and diamine or corresponding trimethylsilylated diamine or the like as a diamine component in a reaction solvent. be able to. The polyamic acid may be one in which a carboxy group forms a salt with an alkali metal ion, ammonium ion, or imidazolium ion, and is a hydrocarbon group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms. Esterified with may be used. On the other hand, polyimide is obtained by imidizing polyamic acid by a method described later.

  There is no restriction | limiting in particular as a reaction solvent, A well-known thing can be used. Examples include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N , N-dimethylpropionamide, γ-butyrolactone, ethyl lactate, 1,3-dimethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, 1,1,3,3-tetramethylurea, dimethylsulfoxide, Use sulfolane, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, water, or the reaction solvent described in International Publication No. 2017/099183, alone or in combination of two or more. Door can be.

  It is preferable to adjust the usage-amount of a reaction solvent so that the total amount of tetracarboxylic acid and a diamine compound may be 0.1-50 mass% of the whole reaction solution. Moreover, -20 degreeC-150 degreeC is preferable and, as for reaction temperature, 0-100 degreeC is more preferable. Furthermore, the reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours. Moreover, it is preferable that the number of moles of the diamine compound used in the reaction is equal to the number of moles of the tetracarboxylic acid. If they are equal, a resin film having high mechanical properties can be easily obtained from the resin composition.

  The obtained polyamic acid solution may be used as it is as the resin composition of the present invention. In this case, the target resin composition can be obtained without isolating the resin by using the same solvent as the resin composition used for the reaction solvent or adding a solvent after the reaction is completed.

  The obtained polyamic acid may be further imidized or esterified with some or all of the repeating units of the polyamic acid. In this case, the polyamic acid solution obtained by polymerization of the polyamic acid may be used as it is for the next reaction, or may be used for the next reaction after the polyamic acid is isolated.

  In the esterification and imidation reactions, the same resin as the resin composition used as the reaction solvent is used as the reaction solvent, or the solvent is added after completion of the reaction, so that the desired resin composition is obtained without isolating the resin. Can be obtained.

  The imidization method is preferably a method of heating the polyamic acid or a method of adding a dehydrating agent and an imidization catalyst and heating as necessary. In the case of the latter method, a process for removing the reaction product of the dehydrating agent, the imidization catalyst, and the like is required, and therefore the former method is more preferable. There is no restriction | limiting in particular as a dehydrating agent and an imidation catalyst, A well-known thing can be used.

  Examples of the reaction solvent used for imidization include the reaction solvents exemplified in the polymerization reaction.

  The reaction temperature of the imidization reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours. By appropriately adjusting the reaction temperature and reaction time within such ranges, a desired ratio of the polyamic acid can be imidized.

  The method of esterifying is preferably a method of reacting an esterifying agent or a method of reacting an alcohol in the presence of a dehydrating condensing agent. There is no restriction | limiting in particular in the material and reaction conditions used for esterification, A well-known thing can be used.

  The varnish obtained by these production methods is preferably filtered using a filter to remove foreign substances such as dust.

<Method for producing resin film>
A method for producing a resin film using the resin composition of the present invention comprises a step of applying the resin composition to a support and a step of heating the coating film to form a resin film on the support. Including.

  First, varnish which is one of the embodiments of the resin composition of the present invention is applied on a support. Examples of the support include a wafer substrate such as silicon and gallium arsenide, a glass substrate such as sapphire glass, soda lime glass, and alkali-free glass, a metal substrate such as stainless steel and copper, a metal foil, and a ceramic substrate. Among these, alkali-free glass is preferable from the viewpoint of surface smoothness and dimensional stability during heating.

  Examples of varnish coating methods include spin coating, slit coating, dip coating, spray coating, and printing, and these may be combined. When the resin film is used as a substrate for a display device or a light receiving device, it is necessary to apply the resin film on a large-sized support, and therefore a slit coating method is particularly preferably used.

  Prior to application, the support may be pretreated in advance. For example, a solution in which 0.5 to 20% by mass of a pretreatment agent is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate is used. Examples thereof include a method of treating the surface of the support by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment. If necessary, a reduced-pressure drying treatment is performed, and then the reaction between the support and the pretreatment agent can be advanced by a heat treatment at 50 ° C to 300 ° C.

  After application, the varnish coating film is generally dried. As a drying method, vacuum drying, heat drying, or a combination thereof can be used. As a method for drying under reduced pressure, for example, a support body on which a coating film is formed is placed in a vacuum chamber, and the inside of the vacuum chamber is decompressed. Heat drying is performed using a hot plate, oven, infrared rays or the like. When a hot plate is used, the coating film is held directly on the plate or on a jig such as a proxy pin installed on the plate and dried by heating.

  When the resin composition of the present invention contains a photoacid generator, a pattern can be formed from the dried coating film by the method described below. The coating film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. . When it has positive photosensitivity, the exposed portion is dissolved in the developer. When it has negative photosensitivity, the exposed area is cured and insolubilized in the developer.

  After exposure, a desired pattern is formed using a developer by removing an exposed portion in the case of a positive type and a non-exposed portion in the case of a negative type. There is no restriction | limiting in particular as a developing solution, A well-known thing can be used (For example, the developing solution etc. which are described in international publication 2017/099183). Of these, aqueous solutions of tetramethylammonium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and other alkaline compounds are preferred for both positive and negative types. In the negative type, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, An organic solvent such as methyl isobutyl ketone can also be used. After development, it is common to rinse with water.

  Finally, a heat-resistant resin film can be produced by heat treatment in the range of 180 ° C. or more and 600 ° C. or less and baking the coating film.

  When the resin film obtained through the above steps is used as a substrate of a display device or a light receiving device, it is usually used in the next step without being peeled off. However, the resin film peeled from the substrate by a peeling method described later may be used to proceed to the next step. When used in the next step without peeling, it is preferable that the generated stress is less than 25 MPa in order to prevent the process passability from being lowered due to warping of the support. The stress is generally measured using a thin film stress measuring device. The mechanism is calculated from the amount of warpage of the substrate on which the polyimide film is formed. In addition, since it will affect a measurement result if a polyimide film absorbs moisture, the result measured in the state which dried the polyimide film is employ | adopted.

  The resin film obtained from the resin composition of the present invention can be used as a member of various electronic devices. In particular, it is suitably used as a substrate for a display device such as an organic EL display, a liquid crystal display, a micro LED display, and electronic paper, a display device member such as a touch panel and a color filter, and a light receiving device such as a solar cell. Conventionally, these devices have been manufactured by using a large-area glass as a substrate and forming various elements thereon. If a glass substrate is used as a support, various elements are similarly formed on the resin film obtained by applying a resin composition, heating and curing, and then removing the glass substrate at the final stage, the resin film is formed into a substrate. Can be manufactured. In particular, since the resin film obtained from the present invention has low stress, even if a large-area glass substrate is a support, warping is small. In addition, as described later, since the glass substrate can be easily removed, it is suitably used for these applications.

  The film thickness of the resin film in the present invention is not particularly limited, but the film thickness is preferably 3 μm or more. More preferably, it is 5 micrometers or more, More preferably, it is 7 micrometers or more. The film thickness is preferably 100 μm or less. More preferably, it is 50 micrometers or less, More preferably, it is 30 micrometers or less. If the film thickness is 3 μm or more, sufficient mechanical properties as a substrate for a display device or a light receiving device can be obtained. If the film thickness is 30 μm or less, sufficient toughness can be obtained as a substrate for a display device or a light receiving device.

<Method for manufacturing display device or light receiving device>
In the method for producing a display device or a light receiving device using the resin composition of the present invention, a step of applying the resin composition to a support, and heating the coating film to form a resin film on the support And a step of forming a display device or a light receiving device on the resin film.

  First, a resin film is manufactured on a support such as a glass substrate by the method described above. At this time, a primer layer may be provided on the support in advance in order to facilitate peeling from the support described later. For example, it is possible to apply a release agent or provide a sacrificial layer on the support. Examples of the release agent include silicone-based, fluorine-based, aromatic polymer-based, alkoxysilane-based and the like. Examples of the sacrificial layer include a metal film, a metal oxide film, and an amorphous silicon film.

  An inorganic film is provided on the resin film as necessary. Accordingly, it is possible to prevent moisture and oxygen from passing through the resin film from the outside of the substrate and causing deterioration of the pixel driving element and the light emitting element. Examples of the inorganic film include silicon oxide (SiOx), silicon nitride (SiNy), silicon oxynitride (SiOxNy), and the like, and these can be used as a single layer or a stack of a plurality of types. Further, these inorganic films can be used by alternately laminating organic films such as polyvinyl alcohol. These inorganic films are preferably formed using a vapor deposition method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD).

  A substrate for a display device or a light receiving device comprising a plurality of layers of inorganic films or resin films can be manufactured by forming a resin film on the inorganic film as necessary or further forming an inorganic film. it can. In addition, it is preferable that the resin composition used for manufacture of each resin film is the same resin composition from a viewpoint of simplification of a process.

  Subsequently, the constituent elements of the display element or the light receiving element are formed on the obtained heat-resistant resin film (or further, if an inorganic film or the like is present thereon). For example, in the case of an organic EL display, an image display element is formed by sequentially forming an image driving element TFT, a first electrode, an organic EL light emitting element, a second electrode, and a sealing film. In the case of a color filter substrate, after forming a black matrix as necessary, colored pixels such as red, green, and blue are formed. In the case of a touch panel substrate, a wiring layer and an insulating layer are formed.

  Finally, the support is removed by peeling both at the interface between the support and the heat-resistant resin film. Examples of the peeling method include the above-described laser lift-off, mechanical peeling method, and etching method of the support. When performing laser lift-off, a laser beam is irradiated to a support such as a glass substrate from the side opposite to the side where the heat-resistant resin film and the element are formed. Thereby, peeling can be performed without damaging the element.

As the laser light, laser light having a wavelength range from ultraviolet light to infrared light can be used, and ultraviolet light is particularly preferable. More preferably, a 308 nm excimer laser is preferable. Peeling energy is preferably 250 mJ / cm ² or less, 200 mJ / cm ² or less being more preferred.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated, this invention is not limited by these examples.

(1) Preparation of polyimide film Using a spin coater (1H-DX2 manufactured by Mikasa Co., Ltd.), a polyimide varnish was spin coated on an 8-inch glass substrate, followed by a hot plate (HPD-3000BZN manufactured by ASONE Co., Ltd.). Used and dried at 110 ° C. for 10 minutes. Subsequently, using an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), the temperature was raised from 50 ° C. to 4 ° C./min under a nitrogen atmosphere (oxygen concentration 20 ppm or less), and heated at 300 ° C. for 30 minutes. A polyimide film having a thickness of 10 μm was formed on a glass substrate.

(2) Measurement of weight average molecular weight Using a part of the varnish obtained in the synthesis example, N-methyl-2-pyrrolidone was used so that the resin content would be 0.05 to 0.1% by mass. Diluted to obtain a measurement sample. The measurement sample was analyzed using gel permeation chromatography (alliance HPLC manufactured by Waters Corporation) under the following conditions to determine the weight average molecular weight (standard polystyrene conversion) of the resin.

  Developing solution: 2.08 g of lithium chloride and 4.80 g of phosphoric acid dissolved in 980 g of N-methyl-2-pyrrolidone were used.

Developing solution flow rate: 0.4 mL / min
Column: TSK guard column, TSK-GEL a-4000, TSK-GEL a-2500 (all manufactured by Tosoh Corporation) were used in series.

Column temperature: 50 ° C
Measurement wavelength: 260 nm.

(3) Measurement of stress Using a thin film stress measuring apparatus (FLX3300-T manufactured by Toago Technology Co., Ltd.), the amount of warpage of the glass substrate on which the polyimide film was formed was measured, and the stress was calculated. In order to eliminate the influence of moisture absorption of the polyimide film, the measurement was performed without exposing to the outside air after drying in the measuring apparatus using the following conditions.

  Heating conditions: The temperature was raised from room temperature to 150 ° C. over 30 minutes, and after reaching 150 ° C., it was cooled to 30 ° C. or lower.

Heating atmosphere: Nitrogen (4) Laser lift-off (LLO)
Using a laser oscillator (manufactured by Coherent, Inc.) having a wavelength of 308 nm, laser irradiation was performed on the glass substrate on which the polyimide film was formed from the side on which the polyimide film was not formed. At this time, the frequency of the laser was 300 Hz, and the area irradiated by one irradiation was 287 mm long × 0.4 mm wide. Irradiation was performed while moving the irradiation area in the width direction by 0.2 mm / time, and the minimum irradiation energy required for the polyimide film to peel from the glass substrate was determined.

Hereinafter, abbreviations of compounds used in Examples are described.
PMDA: pyromellitic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride ODPA: 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride DAE: 4, 4′-diaminodiphenyl ether DDS: 4,4′-diaminodiphenylsulfonediamine V: diamine represented by chemical formula (6) (Preamine 1075 manufactured by Croda International plc)
Diamine U: Diamine represented by chemical formula (9) (Preamine 1074, manufactured by Croda Informational plc)
NMP: N-methyl-2-pyrrolidone silicone diamine A: X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Synthesis example 1:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 8.010 g (40.00 mmol) of DAE and 5.346 g (10.00 mmol) of diamine V were added while stirring, and the mixture was washed with 20 g of NMP. After confirming that DAE was dissolved, 14.71 g (50.00 mmol) of BPDA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis example 2:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 10.01 g (50.00 mmol) of DAE was added while stirring and washed with 20 g of NMP. After confirming that the diamine was dissolved, 14.71 g (50.00 mmol) of BPDA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis Example 3:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 8.010 g (40.00 mmol) of DAE and 5.346 g (10.00 mmol) of diamine V were added while stirring, and the mixture was washed with 20 g of NMP. After confirming that the diamine was dissolved, 10.91 g (50.00 mmol) of PMDA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis Example 4:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 10.01 g (50.00 mmol) of DAE was added while stirring and washed with 20 g of NMP. After confirming that the diamine was dissolved, 10.91 g (50.00 mmol) of PMDA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis Example 5:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 9.932 g (40.00 mmol) of DDS and 5.346 g (10.00 mmol) of diamine V were added while stirring, and washed with 20 g of NMP. After confirming that the diamine was dissolved, 15.51 g (50.00 mmol) of ODPA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis Example 6:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 12.42 g (50.00 mmol) of DDS was added while stirring, and washed with 20 g of NMP. After confirming that the diamine was dissolved, 15.51 g (50.00 mmol) of ODPA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis Example 7:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 9.932 g (40.00 mmol) of DDS and 13.40 g (10.00 mmol) of silicone diamine A were added while stirring, and washed with 20 g of NMP. After confirming that the diamine was dissolved, 15.51 g (50.00 mmol) of ODPA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Synthesis Example 8:
A varnish was obtained in the same manner as in Synthesis Example 5, except that an operation of reacting at 60 ° C. for 4 hours and then reacting at 180 ° C. for 4 hours was added.

Synthesis Example 9:
A varnish was obtained in the same manner as in Synthesis Example 6 except that an operation of reacting at 60 ° C. for 4 hours and then reacting at 180 ° C. for 4 hours was added.

Synthesis Example 10:
A thermometer and a stirring rod with stirring blades were set in a 300 mL four-necked flask. Next, 120 g of NMP was added under a dry nitrogen stream, and the temperature was raised to 40 ° C. After raising the temperature, 8.010 g (40.00 mmol) of DAE and 5.310 g (10.00 mmol) of diamine U were added while stirring, and washed with 20 g of NMP. After confirming that DAE was dissolved, 14.71 g (50.00 mmol) of BPDA was added and washed with 20 g of NMP. After raising the temperature to 60 ° C., the reaction was carried out for 4 hours. After cooling, the reaction solution was filtered through a polyethylene filter (filter pore size 0.2 μm) to obtain a varnish.

Examples 1-5, Comparative Examples 1-4
Using the varnishes obtained in Synthesis Examples 1 to 10, a polyimide film was produced on a glass substrate by the above method. The stress measurement and LLO of the polyimide film produced on the glass substrate were implemented by the above method.

  Table 1 shows the stress measurement results of Examples 1 to 5 and Comparative Examples 1 to 4 and the evaluation results of the irradiation energy required for LLO.

Example 101
On the heat resistant resin film obtained in Example 1, a gas barrier film composed of a laminate of SiO ₂ and Si ₃ N ₄ was formed by CVD. Subsequently, a TFT was formed, and an insulating film made of Si ₃ N ₄ was formed so as to cover the TFT. Next, after forming a contact hole in the insulating film, a wiring connected to the TFT through the contact hole was formed.

  Further, a planarization film was formed in order to planarize the unevenness due to the formation of the wiring. Next, a first electrode made of ITO was formed on the obtained flattened film by being connected to the wiring. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and dehydrated by heating to obtain an electrode substrate with a planarizing film. Next, an insulating film having a shape covering the periphery of the first electrode was formed.

Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al / Mg was formed on the entire surface above the substrate. Further, a sealing film made of a laminate of SiO ₂ and Si ₃ N ₄ was formed by CVD. Finally, the glass substrate was irradiated with a laser (wavelength: 308 nm) from the side where the heat resistant resin film was not formed, and peeling was performed at the interface with the heat resistant resin film. The irradiation energy at this time was 200 mJ / cm ² with reference to the results in Table 1.

  As described above, an organic EL display device formed on the heat resistant resin film was obtained. When voltage was applied through the drive circuit, good light emission was exhibited.

Comparative Example 101
Since the heat-resistant resin films obtained in Comparative Examples 1, 2, 3A and 4 have large warpage of the glass substrate and vacuum adsorption could not be performed on the stage of the CVD apparatus, the steps after the formation of the gas barrier film can be performed. There wasn't.

Comparative Example 102
A gas barrier film made of a laminate of SiO ₂ and Si ₃ N ₄ was formed on the heat-resistant resin film obtained in Comparative Example 3B by CVD. Subsequently, a TFT was formed, and an insulating film made of Si ₃ N ₄ was formed so as to cover the TFT. Next, after forming a contact hole in the insulating film, a wiring connected to the TFT through the contact hole was formed.

  Further, a planarization film was formed in order to planarize the unevenness due to the formation of the wiring. Next, a first electrode made of ITO was formed on the obtained flattened film by being connected to the wiring. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped using a resist stripping solution (mixed solution of monoethanolamine and diethylene glycol monobutyl ether). The substrate after peeling was washed with water and dehydrated by heating to obtain an electrode substrate with a planarizing film. Next, an insulating film having a shape covering the periphery of the first electrode was formed.

Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al / Mg was formed on the entire surface above the substrate. Further, a sealing film made of a laminate of SiO ₂ and Si ₃ N ₄ was formed by CVD. Finally, the glass substrate was irradiated with a laser (wavelength: 308 nm) from the side where the heat resistant resin film was not formed, and peeling was performed at the interface with the heat resistant resin film. The irradiation energy at this time was 300 mJ / cm ² with reference to the results in Table 1.

  As described above, an organic EL display device formed on the heat resistant resin film was obtained. Although voltage was applied via the drive circuit, there was an area that did not light up due to damage by the laser.

Claims (10)

A resin composition comprising a resin having a repeating unit represented by chemical formula (1) or (2) as a main component and used as a substrate of a display device or a light receiving device.

(In the chemical formulas (1) and (2), X represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms, and Y represents a divalent diamine residue having 2 or more carbon atoms. However, in the resin, 1 mol% or more of all X and Y has a structure in which at least 4 or more hydrogen atoms of an alicyclic hydrocarbon having 4 to 8 carbon atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms. A tetravalent tetracarboxylic acid residue and / or a divalent diamine residue, wherein R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a group having 1 to 10 carbon atoms; Represents an alkylsilyl group, an alkali metal ion, an ammonium ion, an imidazolium ion or a pyridinium ion.) 2. The resin composition according to claim 1, wherein 1 mol% or more of all Y in the resin is a residue of a diamine represented by the chemical formula (5).

(In Chemical Formula (5), m represents an integer of 4 to 8. Each of m Ws independently represents any of the structural units represented by Chemical Formulas (5a) to (5d). Z in the chemical formula (5b) and U in the chemical formula (5c) represent a hydrogen atom or an amino group, and n and k represent any integer of 3 to 11.) The 1 mol% or more of all the Y in the resin is a residue of a diamine represented by any one of the chemical formulas (6) to (9). Resin composition.

  Furthermore, the resin composition in any one of Claims 1-3 containing a solvent. Applying the resin composition according to claim 4 to a support;
Heating the coating film to form a resin film on the support;
Forming a display device or a light receiving device on the resin film;
Manufacturing method of display device or light receiving device including   Furthermore, the manufacturing method of the display device or light receiving device of Claim 5 including the process of removing the said support body. A substrate for a display device or a light-receiving device, comprising a resin whose main component is a repeating unit represented by chemical formula (1).

(In the chemical formula (1), X represents a tetravalent tetracarboxylic acid residue having 2 or more carbon atoms, and Y represents a divalent diamine residue having 2 or more carbon atoms. 1 mol% or more of X and Y has a structure in which at least 4 or more hydrogen atoms of an alicyclic hydrocarbon having 4 to 8 carbon atoms are substituted with a hydrocarbon group having 4 to 12 carbon atoms. A tetravalent carboxylic acid residue and / or a divalent diamine residue.) The substrate according to claim 7, wherein 1 mol% or more of all Y in the resin is a residue of a diamine represented by the chemical formula (5).

(In Chemical Formula (5), m represents an integer of 4 to 8. Each of m Ws independently represents any of the structural units represented by Chemical Formulas (5a) to (5d). Z in the chemical formula (5b) and U in the chemical formula (5c) represent a hydrogen atom or an amino group, and n and k represent any integer of 3 to 11.) 9% or more of all Y in the resin is a residue of a diamine represented by any one of chemical formulas (6) to (9). substrate.

  A display device or a light receiving device in which a display element or a light receiving element is formed on the substrate according to claim 7.