Positive photosensitive resin composition

Abstract

This positive photosensitive resin composition comprises: (A) component; not less than 35.0 parts by mass to less than 90.0 parts by mass of (B) component with respect to 100 parts by mass of the (A) component; (C) component; and (D) component.　(A) component: A polyester including a structural unit represented by formula (1) (B) component: A vinyl ether compound represented by formula (2) or formula (3) (C) component: A photoacid generator (D) component: A solvent (In formula (1), X represents a tetravalent organic group. Y represents a divalent organic group.) (In formula (2), k represents an integer of 1-10. m1 represents an integer of 2-6.　In formula (3), m2 represents an integer of 2-10.)

Description

Positive-type photosensitive resin composition

[0001] The present invention relates to a positive-type photosensitive resin composition and a method for manufacturing a light-emitting display device using the composition.

[0002] In recent years, inorganic EL devices using quantum dot light-emitting diode (QLED) technology and organic EL devices using organic light-emitting diode (OLED) technology have been developed as light-emitting display devices.

[0003] For example, quantum dots possess high luminescence and a narrow emission spectrum, the ability to tune their emission wavelength to a single excitation wavelength, and unique properties that make them stable with respect to light. Therefore, much research is being conducted on their use in important application fields such as biological imaging, energy conversion, and lighting (LEDs). Many inventions have also been made concerning quantum dots and electronic devices containing quantum dots in their light-emitting layers. For instance, a light-emitting display device using quantum dot light-emitting diode technology as an electronic device has been proposed (see, for example, Patent Document 1).

[0004] Japanese Patent Publication No. 2022-112507

[0005] When manufacturing the light-emitting layer of a light-emitting display device using photolithography, the photoresist composition (photosensitive resin composition) used in photolithography may be required to have properties such as the ability to form a film with good solvent resistance at relatively low temperatures and good adhesion of the film formed from the composition to the functional layer.

[0006] In view of the above circumstances, the object of the present invention is to provide a positive-type photosensitive resin composition that can form a film with good solvent resistance by film formation at a relatively low temperature and has good adhesion to the functional layer of the formed film, and a method for manufacturing a light-emitting display device using the composition.

[0007] The inventors of the present invention conducted diligent research to solve the aforementioned problems and, as a result, found that they could solve the aforementioned problems, and completed the present invention having the following gist. That is, the present invention encompasses the following.

[0008] [1] A positive-type photosensitive resin composition containing the following component (A), component (B) in an amount of 35.0 parts by mass or more and less than 90.0 parts by mass per 100 parts by mass of component (A), component (C), and component (D). (A) component: polyester containing a structural unit represented by the following formula (1) (B) component: vinyl ether compound represented by the following formula (2) or formula (3) (C) component: photoacid generator (D) component: solvent (In formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group.) (In formula (2), k represents an integer from 1 to 10. m1 represents an integer from 2 to 6. In formula (3), m2 represents an integer from 2 to 10.) [2] The positive-type photosensitive resin composition according to [1], wherein the component (A) is obtained by reacting a reaction material containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol represented by the following formula (ii). (In formula (i), X represents a tetravalent organic group. In formula (ii), Y represents a divalent organic group.) [3] The positive-type photosensitive resin composition according to [1] or [2], wherein X represents a tetravalent organic group represented by any of the following formulas (X-1) to (X-16), and Y represents a divalent organic group represented by any of the following formulas (Y-1) to (Y-10). (In the formula, n1 represents an integer from 1 to 4. n2 represents an integer from 1 to 7. * represents a bond.) [4] The positive-type photosensitive resin composition according to any one of [1] to [3], wherein the component (A) has a terminal group represented by the following formula (E1) or formula (E2). (In formula (E1), R １ R represents a monovalent organic residue obtained by removing a hydroxyl group from a monoalcohol. * represents a bond. In formula (E2), R ２represents a divalent organic residue obtained by removing the acid anhydride structure from a dicarboxylic acid anhydride. * represents a bond.) [5] The positive-type photosensitive resin composition according to any one of [1] to [4], wherein the weight-average molecular weight of component (A) is 1,000 or more and 30,000 or less. [6] The positive-type photosensitive resin composition according to any one of [1] to [5], wherein the content of component (C) is 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of component (A). [7] The positive-type photosensitive resin composition according to any one of [1] to [6], further containing the following component (E). (E) component: surfactant [8] The positive-type photosensitive resin composition according to any one of [1] to [7], used in the manufacture of light-emitting display devices. [9] A method for manufacturing a light-emitting display device, comprising the steps of: applying a positive-type photosensitive resin composition according to any one of [1] to [8] onto a functional layer, heating it to form a cured photosensitive resin layer; exposing the cured photosensitive resin layer to light and developing it through a photomask to form a patterned photosensitive resin layer having openings; and forming a light-emitting region on the exposed functional layer within the openings of the patterned photosensitive resin layer.

[10] The method for manufacturing a light-emitting display device according to [9], wherein the light-emitting region includes quantum dots.

[0009] According to the present invention, it is possible to provide a positive-type photosensitive resin composition that can form a film with good solvent resistance by forming the film at a relatively low temperature, and that has good adhesion to the functional layer of the formed film, and a method for manufacturing a light-emitting display device using the composition.

[0010] Figure 1 is a schematic cross-sectional view of an example of a light-emitting display device. Figure 2 is a schematic cross-sectional view of another example of a light-emitting display device. Figure 3 is a schematic cross-sectional view of yet another example of a light-emitting display device.

[0011] (Positive-type photosensitive resin composition) The positive-type photosensitive resin composition of the present invention contains the following component (A), component (B), component (C), and component (D). The positive-type photosensitive resin composition may also contain other components.

[0012] (A) Component: Polyester containing structural units represented by the following formula (1) (B) Component: Vinyl ether compound represented by the following formula (2) or formula (3) (C) Component: Photoacid generator (D) Component: Solvent (In formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group.) (In equation (2), k represents an integer from 1 to 10. m1 represents an integer from 2 to 6. In equation (3), m2 represents an integer from 2 to 10.)

[0013] <Component (A): Polyester> Component (A), polyester, contains structural units represented by the following formula (1). (In formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group.)

[0014] <<X>> In formula (1), X is not particularly limited as long as it is a tetravalent organic group. The number of carbon atoms in the tetravalent organic group may be, for example, 1 to 40, 2 to 35, or 4 to 30. X may or may not have a ring structure, but it is preferable that it has a ring structure. The ring structure may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. The hydrocarbon ring may be an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. Examples of aliphatic hydrocarbon rings include cyclobutane rings, cyclopentane rings, and cyclohexane rings. If X has a ring structure, the number of ring structures X has may be one, two, three, or four. X may have heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. From the viewpoint of suitably obtaining the effects of the present invention, X is preferably a tetravalent organic group represented by any of the following formulas (X-1) to (X-16). (In the formula, * represents a bond.)

[0015] <<Y>> In formula (1), Y is not particularly limited as long as it is a divalent organic group. The number of carbon atoms in the divalent organic group may be, for example, 1 to 40, 2 to 30, or 4 to 20. Y may or may not have a ring structure. The ring structure may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. The hydrocarbon ring may be an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include a benzene ring and a naphthalene ring. Examples of aliphatic hydrocarbon rings include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring. If Y has a ring structure, the number of ring structures that Y has may be one, two, three, or four. Y may have heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. From the viewpoint of suitably obtaining the effects of the present invention, Y is preferably a divalent organic group represented by any of the following formulas (Y-1) to (Y-10). (In the formula, n1 represents an integer from 1 to 4. n2 represents an integer from 1 to 7. * represents a combination.)

[0016] The polyester component (A) may have terminal groups represented by the following formula (E1) or formula (E2). (In formula (E1), R １ R represents a monovalent organic residue obtained by removing a hydroxyl group from a monoalcohol. * represents a bond. In formula (E2), R ２ represents a divalent organic residue obtained by removing the acid anhydride structure from a dicarboxylic acid anhydride. * represents a bond.

[0017] R in equation (E1) １represents a monovalent organic residue obtained by removing a hydroxyl group from a monoalcohol. The number of carbon atoms in a monovalent organic residue is not particularly limited and may be, for example, 1 to 40, 2 to 30, or 4 to 20. A monovalent organic residue may or may not have a ring structure. The ring structure may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. The hydrocarbon ring may be an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. Examples of aliphatic hydrocarbon rings include cyclobutane rings, cyclopentane rings, and cyclohexane rings. A monovalent organic residue may have a heteroatom. Examples of heteroatoms include oxygen, nitrogen, sulfur, and halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of monoalcohols used here include 2-phenoxyethanol, 3-phenyl-1-propanol, 2-phenylethyl alcohol, benzyl alcohol, diethylene glycol monophenyl ether, ethylene glycol monomethyl ether, 2-(4-methylphenoxy)ethanol, 2-(3-methylphenoxy)ethanol, 1-(4-methylphenoxy)-2-propanol, 4-(2-hydroxyethoxy)methyl benzoate, 2-hydroxy-3-phenoxypropyl acrylate, 2-(pentafluorophenoxy)ethanol, 1-butanol, and 1-hexanol.

[0018] R in equation (E2) ２represents a divalent organic residue obtained by removing the acid anhydride structure from a dicarboxylic acid anhydride. The number of carbon atoms in the divalent organic residue is not particularly limited and may be, for example, 1 to 40, 2 to 30, or 4 to 20. The divalent organic residue may or may not have a ring structure. The ring structure may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferred. The hydrocarbon ring may be an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings. Examples of aliphatic hydrocarbon rings include cyclobutane rings, cyclopentane rings, and cyclohexane rings. The divalent organic residue may have a heteroatom. Examples of heteroatoms include oxygen, nitrogen, sulfur, and halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms. Examples of dicarboxylic acid anhydrides used here include phthalic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, 4-methyl-1,2-cyclohexanedicarboxylic acid anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic acid anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, and bicyclo[2.2.2.]octen-2,3-dicarboxylic acid anhydride.

[0019] The polyester component (A) can be obtained, for example, by reacting a reaction material containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol represented by the following formula (ii). (In formula (i), X represents a tetravalent organic group. In formula (ii), Y represents a divalent organic group.)

[0020] Examples and preferred examples of X in formula (i) include, for example, the examples and preferred examples of X in formula (1), respectively. Examples and preferred examples of Y in formula (ii) include, for example, the examples and preferred examples of Y in formula (1), respectively.

[0021] In addition, the reaction raw material may contain, for example, a compound represented by the following formula (E1-1) or formula (E2-1). That is, the polyester that is component (A) is obtained by reacting a reaction raw material containing a tetracarboxylic acid represented by formula (i), a diol represented by formula (ii), and a compound represented by the following formula (E1-1) or formula (E2-1). For example, when the reaction raw material contains a compound represented by the following formula (E1-1), a terminal group represented by formula (E1) is introduced into a terminal of the obtained polyester. For example, when the reaction raw material contains a compound represented by the following formula (E2-1), a terminal group represented by formula (E2) is introduced into a terminal of the obtained polyester. (In formula (E1-1), R １ represents a monovalent organic group. In formula (E2-1), R ２ represents a divalent organic group.)

[0022] Examples and preferred examples of R １ in formula (E1-1) include the examples and preferred examples of R １ in formula (E1), respectively. Examples and preferred examples of R ２ in formula (E2-1) include the examples and preferred examples of R ２ in formula (E2), respectively.

[0023] The proportion of the structural unit represented by formula (1) in the polyester that is component (A) is not particularly limited, and may be, for example, 60% by mass or more, 70% by mass or more, or 80% by mass or more.

[0024] The polyester that is component (A) is, for example, not a polyester amic acid. That is, the polyester that is component (A) does not have an amide bond, for example.

[0025] (A) The method for producing the polyester component is not particularly limited, but includes reacting a tetracarboxylic dianhydride, a diol, and, if necessary, a monoalcohol or dicarboxylic anhydride. Examples of tetracarboxylic dianhydrides include the tetracarboxylic dianhydride represented by formula (i). Examples of diols include the diol represented by formula (ii). Examples of monoalcohols include the monoalcohol represented by formula (E1-1). Examples of dicarboxylic anhydrides include the dicarboxylic anhydride represented by formula (E2-1).

[0026] There are no particular restrictions on the order of addition during the reaction.

[0027] The reaction is carried out, for example, in the presence of a solvent. Examples of solvents include the solvent described later as component (D).

[0028] The reaction temperature is not particularly limited, but for example, it can range from 60°C to 120°C. The reaction time is not particularly limited, but for example, it can range from 1 hour to 48 hours.

[0029] A catalyst may be used during the reaction. Examples of catalysts include the following. There are no particular restrictions on the amount of catalyst used. Triphenylphosphine, tributylphosphine, tris(4-methylphenyl)phosphine, tris(4-nonylphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(2,6-dimethoxyphenyl)phosphine, triphenylphosphine, triphenylborane, and other phosphines, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra(4-methylphenyl)borate, tetraphenylphosphonium Quaternary phosphonium salts such as traphenylphosphonium tetra(4-methoxyphenyl)borate and tetraphenylphosphonium tetra(4-fluorophenyl)borate; quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, and tetrapropylammonium bromide.

[0030] The weight-average molecular weight of the polyester component (A) is not particularly limited, but is preferably 1,000 to 30,000, more preferably 1,000 to 20,000, even more preferably 1,200 to 15,000, and particularly preferably 1,200 to 10,000. The weight-average molecular weight can be determined by gel permeation chromatography (GPC) measurement.

[0031] The content of component (A) in the positive-type photosensitive resin composition is not particularly limited, but is preferably 40% to 90% by mass, and more preferably 50% to 80% by mass, relative to the film constituent components. Film constituent components refer to components other than the solvent in the positive-type photosensitive resin composition.

[0032] <Component (B): Vinyl ether compound> The vinyl ether compound of component (B) is represented by the following formula (2) or formula (3). (In equation (2), k represents an integer from 1 to 10. M1 represents an integer from 2 to 6. In equation (3), m2 represents an integer from 2 to 10.)

[0033] The vinyl ether group of the vinyl ether compound of component (B) reacts with the carboxyl group of the polyester of component (A) at a conventional pre-bake temperature to form a hemiacetal ester structure. As a result, thermal crosslinking is possible. After thermal crosslinking, the vinyl ether compound is separated (decrosslinked) from the polyester of component (A) by the acid generated by exposure in the presence of a photoacid generator, and then removed together with the polyester of component (A) by development using an alkaline developer.

[0034] k represents an integer from 1 to 10, preferably from 2 to 6. m1 represents an integer from 2 to 6, preferably from 2 to 4, and more preferably from 2 or 3. Furthermore, m1 is particularly preferred if it is 3, as this results in better adhesion of the formed film to the functional layer. m2 represents an integer from 2 to 10, preferably from 2 to 4, and more preferably from 2 or 3.

[0035] (B) Preferably, the component is tris(4-(vinyloxy)butyl) trimellitate, bis(4-(vinyloxy)butyl) terephthalate, bis(4-(vinyloxy)butyl) isophthalate, or 1,4-cyclohexanedimethanol divinyl ether.

[0036] The content of component (B) in the positive-type photosensitive resin composition is 35.0 parts by mass or more and less than 90.0 parts by mass per 100 parts by mass of polyester component (A). If the content is less than 35.0 parts by mass, the adhesion of the formed film to the functional layer is poor, and if the content is 90.0 parts by mass or more, the solvent resistance of the formed film is poor. From the viewpoint of obtaining better adhesion of the formed film to the functional layer, the content of component (B) per 100 parts by mass of polyester component (A) is preferably 37.5 parts by mass or more, more preferably 50.0 parts by mass or more, and particularly preferably 65.0 parts by mass or more. From the viewpoint of obtaining better solvent resistance of the formed film, the content of component (B) per 100 parts by mass of polyester component (A) is preferably 87.5 parts by mass or less, and more preferably 85.0 parts by mass or less.

[0037] <(C) Component: Photoacid Generator> Component (C) is a photoacid generator (PAG). This is used in light exposure (ultraviolet rays such as g, h, i rays, ArF, KrF, F ２ A substance that directly or indirectly generates acids (sulfonic acids, carboxylic acids, etc.) upon irradiation with laser light or electron beams, and as long as it possesses such properties, its type and structure are not particularly limited.

[0038] Examples of photoacid generators for component (C) include cyano group-containing oximesulfonate compounds, diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. Any conventionally known or conventionally used photoacid generators can be applied in the present invention without any particular limitations. In the present invention, the photoacid generator for component (C) may be used alone or in combination of two or more types.

[0039] Examples of photoacid generators include the following. These compounds are just a few examples from the very large number of applicable photoacid generators, and are, of course, not the only ones available.

[0040] Examples of cyano group-containing oximesulfonate compounds include the compound represented by the following formula (C). (In formula (C), R １ R represents a halogen atom or a hydrocarbon group which may have substituents. n represents an integer from 0 to 3. ２ (This represents an organic group containing a hydrogen atom, a halogen atom, a hydrocarbon group which may be substituted with a halogen atom, or a ketone group.)

[0041] R １ Examples of halogen atoms in this context include chlorine atoms and fluorine atoms. １ Examples of hydrocarbon groups in the "optionally substituted hydrocarbon group" include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. The number of carbon atoms in the hydrocarbon group can be, for example, 1 to 10. The hydrocarbon group may be linear, branched, or cyclic, and may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. １ Preferably, the hydrocarbon group is a linear or branched chain having 1 to 4 carbon atoms.

[0042] n represents an integer from 0 to 3, preferably 0 or 1. When n is 2 or 3, multiple R １ They may be the same or they may be different.

[0043] R ２ Examples of halogen atoms in this context include chlorine atoms and fluorine atoms. ２ Examples of hydrocarbon groups in "hydrocarbon groups that may be substituted with halogen atoms" include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups that may be substituted with alkyl groups. Examples of the number of carbon atoms in the hydrocarbon group include 1 to 10. Examples of hydrocarbon groups substituted with halogen atoms include alkyl halides and aryl groups substituted with alkyl halides. ２ Examples of organic groups containing a ketone group in this context include the monovalent group represented by the following formula. (* indicates a link.)

[0044] Examples of cyano group-containing oximesulfonate compounds include the following compounds:

[0045] Examples of commercially available cyano group-containing oximesulfonate compounds include Irgacure PAG103, Irgacure PAG108, Irgacure PAG121, and Irgacure PAG203, all manufactured by BASF Japan.

[0046] Other photoacid generators include, for example, the following compounds: diphenyliodonium chloride, diphenyliodonium trifluoromethanesulfate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexafluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfate, bis(p-tert-butylphenyl)iodonium tetrafluoroborate, bis(p-tert-butylphenyl)iod Nium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate, triphenylsulfonium chloride, triphenylsulfonium bromide, triphenylsulfonium trifluoromethanesulfonate, tri(p-methoxyphenyl)sulfonium tetrafluoroborate, tri(p-methoxyphenyl)sulfonium hexafluorophosphonate, tri(p-ethoxyphenyl)sulfonium tetrafluoroborate, triphenylphosphonium chloride, triphenylphosphonium bromide, tri(p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate, compounds with the following structures

[0047] In the present invention, one photoacid generator selected from the above-mentioned group of compounds can be used alone, or two or more photoacid generators selected from the above-mentioned group of compounds can be used in combination.

[0048] The content of component (C) in the positive-type photosensitive resin composition is not particularly limited, and for example, it is 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of polyester component (A).

[0049] From the viewpoint of forming a good pattern, the content of component (C) relative to 100 parts by mass of polyester of component (A) is preferably 50.0 parts by mass or less, more preferably 30.0 parts by mass or less, and particularly preferably 10.0 parts by mass or less.

[0050] <Component (D): Solvent> The solvent of component (D) used in the present invention dissolves components (A) to (C), and also dissolves component (E) and other components described later, which may be added as desired. The type and structure of the solvent are not particularly limited as long as it has such dissolving ability.

[0051] Examples of solvents for component (D) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, and 2-heptanone. Examples include γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0052] These solvents can be used individually or in combination of two or more.

[0053] Among these components (D), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, and butyl lactate are preferred from the viewpoint of good film-forming properties and high safety. These solvents are generally used as solvents for photoresist materials.

[0054] The solvent content in the positive-type photosensitive resin composition is not particularly limited, but is preferably 50% to 99% by mass, more preferably 60% to 95% by mass, and particularly preferably 70% to 90% by mass.

[0055] <Other components> The positive-type photosensitive resin composition may further contain, for example, component (E) below, as other components.

[0056] <<(E) Component: Surfactant>> Positive-type photosensitive resin compositions may also contain surfactants for the purpose of improving coatability. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and nonioethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Fluorine-based surfactants, F-Top® EF301, EF303, EF352 (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MEGAFACE® F171, F173, R-30, R-40, R-40-LM, EFS-131, EFS-321, EFS-521, EFS-801 (all manufactured by DIC Corporation), Florard FC430, FC431 (both manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard® AG710, Surflon® S-382 Examples include fluorinated surfactants such as SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.), DFX-18, FTX-206D, FTX-212D, FTX-218, FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, and other Futergent series (manufactured by Neos Co., Ltd.), as well as organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants can be used individually or in combination of two or more.

[0057] Furthermore, when the surfactant is used, its content in the positive-type photosensitive resin composition is not particularly limited, and is, for example, 0.0001% to 3% by mass, preferably 0.001% to 1% by mass, and more preferably 0.01% to 0.5% by mass, relative to the film constituent components.

[0058] Positive-type photosensitive resin compositions are preferably used in the manufacture of light-emitting display devices.

[0059] (Method for manufacturing a light-emitting display device) The method for manufacturing a light-emitting display device of the present invention comprises a first step, a second step, and a third step, and further steps as necessary. The first step is to apply the positive-type photosensitive resin composition of the present invention onto a functional layer, heat it, and form a cured photosensitive resin layer. The second step is to expose the cured photosensitive resin layer through a photomask and develop it to form a patterned photosensitive resin layer having openings. The third step is to form light-emitting regions on the exposed functional layer within the openings of the patterned photosensitive resin layer.

[0060] Examples of light-emitting display devices that can be manufactured include quantum dot EL devices (inorganic EL devices) using quantum dot light-emitting diodes (QLEDs) and organic EL devices using organic light-emitting diodes (OLEDs).

[0061] First, one embodiment of a manufactured light-emitting display device will be described. The light-emitting display device includes at least an anode into which holes are injected, a cathode into which electrons are injected, and an EL medium sandwiched between the two electrodes, where holes and electrons are coupled in order to emit light. The light-emitting display device often has a substrate.

[0062] Figure 1 shows a schematic cross-sectional view of an example of a light-emitting display device. Figures 2 and 3 show schematic cross-sectional views of other examples of light-emitting display devices. The light-emitting display device 10, as shown in Figure 1, has an electrode (e.g., anode electrode) 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and an upper electrode (e.g., cathode electrode) 8 on a substrate 1 in this order. The layers between the anode electrode and the cathode electrode are collectively referred to as an EL laminate 9, which includes the light-emitting layer 5 and at least one of the layers from the hole injection layer 3, hole transport layer 4, electron transport layer 6, and electron injection layer 7. It is also possible to add layers known to form a light-emitting display device other than those mentioned above. It is also possible to reduce the number of layers, and for example, as shown in Figure 2, a structure in which the hole injection layer and electron injection layer are appropriately removed may be used. In particular, preferred embodiments of the light-emitting display device shown in Figure 1 include, for example, quantum dot EL devices and organic EL devices. If the light-emitting display device in Figure 1 is a quantum dot EL device, the light-emitting display device 10 has an electrode (e.g., anode electrode) 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and an upper electrode (e.g., cathode electrode) 8 on a substrate 1 in this order. More preferred lamination embodiments of the quantum dot EL device include, for example, a configuration in which an electrode (e.g., anode electrode) 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, and an upper electrode (e.g., cathode electrode) 8 are laminated on a substrate 1, or a configuration in which an electrode (e.g., anode electrode) 2, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, and an upper electrode (e.g., cathode electrode) 8 are laminated on a substrate 1.

[0063] Another example of a light-emitting display device is the one shown in Figure 1, which has a structure in which the positive and negative electrodes are reversed. For example, the light-emitting display device 10 shown in Figure 3 has, in this order, an electrode (e.g., a cathode electrode) 2', an electron injection layer 3', an electron transport layer 4', a light-emitting layer 5', a hole transport layer 6', a hole injection layer 7', and an upper electrode (e.g., an anode electrode) 8' on a substrate 1'. The layers between the anode electrode and the cathode electrode are collectively referred to as the EL laminate 9'.

[0064] - Substrate - Examples of substrates include glass substrates and plastic substrates. There are no particular restrictions on the size of the substrate. There are no particular restrictions on the thickness of the substrate.

[0065] - Anode Electrode - When electroluminescence (EL) is visible through the anode electrode, the anode electrode is essentially light-transmitting. The anode electrode may also be a transparent electrode. Common transparent anode materials used in the present invention include, for example, indium-tin oxide (ITO), indium-zinc oxide (IZO), and tin oxide. Furthermore, zinc oxide doped with aluminum or indium, magnesium-indium oxide, and nickel-tungsten oxide may also be used, but are not limited to these. In addition to these oxides, metal nitrides such as gallium nitride, metal selenides such as zinc selenide, and metal sulfides such as zinc sulfide can also be used as anodes. If EL is not visible through the anode, for example, several conductive materials known to be usable in organic EL devices can be selected. For example, metals such as aluminum, molybdenum, gold, iridium, silver, and magnesium, the transparent conductive oxides mentioned above, or combinations thereof.

[0066] - Cathode Electrode - The upper electrode (cathode electrode) may be a metal electrode. If the EL is visible through the cathode, then the cathode electrode is transparent or nearly transparent. For this to be the case, the metal must be thin, preferably the thickness of the cathode electrode is less than 25 nm. A transparent conductive oxide (e.g., indium-tin oxide, indium-zinc oxide) may be used for the cathode electrode, or a combination of these materials. If the EL is not visible through the cathode, then several conductive materials known to be usable in organic EL devices can be selected. For example, metals such as aluminum, molybdenum, gold, iridium, silver, and magnesium, the transparent conductive oxides mentioned above, or a combination thereof.

[0067] - Hole Injection Layer - The hole injection layer is formed from one type of material or a mixture of materials. The hole injection layer may be introduced in several layers with different compositions. The hole injection layer may help improve the film formation properties of the subsequent layer and facilitate the injection of holes into the hole injection layer. Suitable materials for use in the hole injection layer include, for example, thiophene-containing compounds, phosphazene compounds, certain aromatic amine compounds, porphyrin compounds, phthalocyanine compounds, etc. The hole injection layer may also contain inorganic compounds such as metal oxides (e.g., molybdenum oxide), metal nitrides, metal carbides, complexes of metal ions and organic ligands, and complexes of transition metal ions and organic ligands.

[0068] - Hole Transport Layer - The hole transport layer may be formed from a single or mixture of organic or inorganic compounds, and may be divided into several layers. The hole transport layer may contain, for example, benzidine, fluorene, carbazole, tertiary arylamine, thiophene, or metal oxides such as nickel oxide, but may instead (or in addition to) contain other electron-rich materials.

[0069] -Emitting Layer- Since there are two types of emissive layers, the emissive layer in inorganic EL devices (e.g., quantum dot EL devices) and the emissive layer in organic EL devices, we will explain each separately.

[0070] --Light-emitting layer in inorganic EL devices (e.g., quantum dot EL devices)-- The light-emitting layer uses quantum dot materials or oxide films. Examples of quantum dot materials include at least one semiconductor nanocrystal selected from the group consisting of II-VI compound semiconductor nanocrystals, III-V compound semiconductor nanocrystals, IV-VI compound semiconductor nanocrystals, and IV compound semiconductor nanocrystals. Examples of II-VI compound semiconductor nanocrystals include binary compounds such as CdSe, CdTe, ZnS, ZnSe, and ZnTe; ternary compounds such as CdSeS, CdSeTe, CdSte, ZnSeS, ZnSeTe, ZnSte, CdZnS, CdZnSe, and CdZnTe; and quaternary compounds such as CdZnSeS, CdZnSeTe, CdZnSte, CdHgSeS, CdHgSeTe, CdHgSte, HgZnSeS, HgZnSeTe, or HgZnSte. Examples of group III-V compound semiconductor nanocrystals include binary compounds such as GaN, GaP, GaAs, GaSb, InP, InAs, or InSb; ternary compounds such as GaNP, GaNAs, GaNSb, GaPAs, GaPSb, InNP, InNAs, InNSb, InPAs, InPSb, or GaAlNP; and quaternary compounds such as GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, or InAlPSb. Examples of IV-VI compound semiconductor nanocrystals include binary compounds such as PbS, PbSe, or PbTe; ternary compounds such as PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, or SnPbTe; and quaternary compounds such as SnPbSSe, SnPbSeTe, or SnPbSTe. Examples of IV compound semiconductor nanocrystals include, but are not limited to, single compounds such as Si and Ge; and binary compounds such as SiC and SiGe.Furthermore, as the semiconductor nanocrystals mentioned above, it is preferable to use materials having a core / shell structure (core / shell nanocrystal) in which a shell is formed with a wide-bandgap semiconductor material, among the combinations of the above materials such as CdSe / ZnS, CdSe / ZnSe, CdTe / ZnS, CdTe / ZnSe, CdSe / CdS, CdS / ZnS, CdS / ZeSe, InP / ZnS, and PbSe / ZnS. The oxide film is preferably composed of an oxide doped with luminescence centers. There are no particular restrictions on the luminescence centers, and transition metal ions or rare earth ions can be appropriately selected depending on the purpose, for example, Ti, Cr, Mn, Cu, W, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, etc. The host oxide can be appropriately selected depending on the purpose, but it is preferable that the band gap energy is greater than or equal to the excitation energy of the luminescence center, and it is also preferable that the band gap energy is greater than or equal to the luminescence energy of the luminescence center. An example of such a host oxide is Al. ２ O ３ Ga ２ O ３ La ２ O ３ , ZrO ２ Examples include YAO (Yttrium Aluminum Oxide), YGO (Yttrium Gadolinium Oxide), and LAO (Lanthanum Aluminum Oxide). The concentration of the luminescent center can be appropriately selected depending on the purpose, but for example, it is preferably 10 atom% or less of the host cation, and particularly preferably 1 to 5 atom%.

[0071] --Emitting Layer in Organic EL Devices-- The emissive layer typically comprises a main material and an emissive dopant. Injected holes and electrons recombine in the emissive layer. The main material includes hole transport layer materials, electron transport layer materials, mixtures of hole transport layer materials and electron transport layer materials, and dipolar materials that already possess the ability to move holes and electrons. Examples of main materials for singlet emission include, but are not limited to, polycyclic aromatic compounds such as anthracene derivatives. Examples of main materials for triplet emission include, but are not limited to, carbazole compounds and aromatic amines. Typical singlet emissive dopants are aromatic organic compounds, and typical triplet emissive dopants are iridium or platinum metal complexes, but are not limited to these.

[0072] The light-emitting layer has light-emitting regions capable of emitting a desired color. For example, the light-emitting layer has three color-emitting regions. For example, the light-emitting layer has a light-emitting region capable of emitting red (R), a light-emitting region capable of emitting green (G), and a light-emitting region capable of emitting blue (B). The number of light-emitting regions of each color in the light-emitting layer is not particularly limited and can be appropriately selected according to, for example, the size and resolution of the light-emitting display device. The size of a single light-emitting region is not particularly limited and can be appropriately selected according to the purpose.

[0073] -Electron Transport Layer- The electron transport layer may be formed from a single or mixture of organic or inorganic compounds. Common electron transport layer materials include metal-oxygen chelates such as Alq, metal oxides such as zinc oxide, magnesium zinc oxide, and tin oxide, phenanthroline derivatives such as BCP, triazenes, benzimidazole, triazole, and oxadiazole, silane compounds such as silacyclopentadiene derivatives, or boron derivatives.

[0074] - Electron injection layer - The electron injection layer may contain an electron transport material and a reducing dopant at or near the boundary between the cathode and the electron transport layer. The reducing dopant may be an organic, inorganic, or metal complex. Typical reducing dopants include alkali metals such as cesium or alkali metal mixtures. The electron injection layer may also contain alkali metal complexes, alkali metal salts, or alkali metal oxides (e.g., lithium quinolates, lithium fluoride, lithium oxide) that form a reducing dopant on top of a cathode material accumulation such as aluminum.

[0075] -Formation of Each Layer- Methods for forming the EL medium material on a substrate include, for example, vapor deposition and coating methods. For example, there are many methods for forming a film of the EL medium material on a substrate, including, but are not limited to, solution coating, vapor deposition, and transfer from a donor sheet. In embodiments of the present invention, some of the functional layers selected from the light-emitting layer, hole injection layer, hole transport layer, electron injection layer, and electron transport layer are formed by vapor deposition, for example, by physical vapor deposition in a reduced pressure environment. However, in the case of a quantum dot light-emitting layer in an inorganic EL device, it is preferable that the light-emitting layer be formed by coating. For example, in the case of an inorganic EL device of quantum dots, each functional layer such as the hole injection layer, hole transport layer, and electron transport layer can be formed by vapor deposition, and the light-emitting layer can be formed by coating. Also, for example, in the case of an inorganic EL device of quantum dots, each functional layer such as the hole injection layer, hole transport layer, and electron transport layer, and the light-emitting layer may be formed by coating. Furthermore, in the case of an organic EL device, for example, each functional layer such as a hole injection layer, a hole transport layer, and an electron transport layer, as well as the light-emitting layer, may be formed by vapor deposition.

[0076] <<<About Quantum Dot EL Devices>>> This section provides a more detailed explanation of quantum dot EL devices, which use quantum dots in their light-emitting layer. A quantum dot (QD) is a nanocrystalline particle whose radius is smaller than or close to the Bohr exciton radius, and whose particle size is typically between 1 and 20 nm. Quantum dots have a quantum confinement effect and can emit fluorescence when excited. Quantum dot EL devices have advantages such as high luminescence efficiency, a wide color range, more realistic color reproduction, and lower energy consumption. A quantum dot EL device includes a light-emitting layer formed from quantum dot material. The quantum dot material is sandwiched between an electron transport layer and a hole transport layer. By introducing a light-emitting layer between the electron transport layer and the hole transport layer, light of a desired wavelength can be obtained. An electric field is applied to the quantum dot EL device to move electrons and holes to the light-emitting layer. In the light-emitting layer, electrons and holes are confined in the quantum dots and combine to emit photons.

[0077] The following describes in detail the manufacturing method of the present invention's light-emitting display device.

[0078] <First Step> The first step involves applying the positive-type photosensitive resin composition of the present invention onto a functional layer, followed by heating to form a cured photosensitive resin layer.

[0079] Examples of functional layers include hole transport layers and electron transport layers.

[0080] The method for applying the positive-type photosensitive resin composition of the present invention is not particularly limited, but suitable application methods such as a spinner or coater can be used. Heating is performed using heating means such as a hot plate or oven. The heating temperature is not particularly limited, but examples include 60°C to 300°C. The positive-type photosensitive resin composition of the present invention yields a cured film with solvent resistance even with low-temperature firing (heating), so the heating temperature is preferably 150°C or lower, and more preferably 120°C or lower. The heating time is not particularly limited, but examples include 0.1 minutes to 360 minutes. The positive-type photosensitive resin composition of the present invention yields a cured film even with short-time firing (heating), so the heating time is preferably 10 minutes or less, and more preferably 5 minutes or less.

[0081] The thickness of the cured photosensitive resin layer is not particularly limited, but for example, it is 0.001 μm to 1000 μm, preferably 0.01 μm to 100 μm, and more preferably 0.1 μm to 10 μm.

[0082] <Second Step> The second step involves exposing the cured photosensitive resin layer to light through a photomask and developing it to form a patterned photosensitive resin layer with openings.

[0083] The exposure light may be laser light or non-laser light. Examples of exposure wavelengths include ultraviolet light (i-line, g-line, and h-line), 193 nm (ArF), 248 nm (KrF), and 157 nm (F). ２ Examples include lasers. Exposure is performed using light having at least one wavelength from i-line, g-line, and h-line, ArF excimer laser light, KrF excimer laser light, or F ２ It is preferable to perform the procedure using laser light. The exposure dose is not particularly limited, for example, 10 mJ / cm². ２ ~1,000mJ / cm ２ These are some examples.

[0084] It is preferable to perform post-exposure baking (PEB) between exposure and development. The heating temperature is not particularly limited, but examples include 80°C to 150°C. The heating time is not particularly limited, but examples include 0.1 minutes to 60 minutes.

[0085] Development is carried out, for example, using an alkaline developer. Examples of alkaline developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, and choline, and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants can be added to these developers. An aqueous solution of 0.1 to 2.38% by mass of tetraethylammonium hydroxide is commonly used as a developer for photoresists, and in the positive-type photosensitive resin composition of the present invention, this alkaline developer can be used to develop it well without causing problems such as swelling. As for the development method, any of the following methods can be used: the liquid-filling method, the dipping method, or the agitation immersion method. The development time in such cases is usually 15 to 180 seconds.

[0086] After developing, rinsing with water may be performed. Examples of suitable water include pure water and deionized water.

[0087] The size of the openings is not particularly limited. The number of openings in the patterned photosensitive resin layer is also not particularly limited and can be appropriately selected, for example, depending on the resolution of the light-emitting display device.

[0088] <Third Step> The third step is to form light-emitting regions on the exposed functional layers within the openings of the patterned photosensitive resin layer.

[0089] The method for forming the light-emitting region is not particularly limited and may be a wet method or a dry method. A wet method, for example, involves applying a coating solution containing a light-emitting material onto the exposed functional layer within the openings of a patterned photosensitive resin layer. A dry method, for example, is vapor deposition.

[0090] The light-emitting region preferably includes quantum dots.

[0091] <Other Processes> Other processes include, for example, the following: Fourth process: A process of peeling off the patterned photosensitive resin layer. Fifth process: A process of repeating the set of the first to fourth processes one or more times.

[0092] <<Fourth Step>> The fourth step is to peel off the patterned photosensitive resin layer. After the light-emitting region is formed in the third step, the patterned photosensitive resin layer is usually peeled off. There are no particular limitations on the peeling method, but one example is to peel the patterned photosensitive resin layer from the functional layer using a peeling solution such as an aqueous sodium hydroxide solution. At this time, unwanted light-emitting materials (e.g., quantum dots) formed on the patterned photosensitive resin layer are also removed.

[0093] <<Fifth Step>> The fifth step is a process in which the set of steps one to four is repeated one or more times. The number of times the set of steps one to four is repeated in the fifth step may be one, two, or three or more times. The emission colors of the emission region of the emission layer are usually three colors: red (R), green (G), and blue (B). The first color emission region is formed in the first four steps before the fifth step is performed. Therefore, the number of times the set of steps one to four is repeated in the fifth step is usually two.

[0094] In the fifth step, the positive-type photosensitive resin composition of the present invention is applied to the functional layer on which the light-emitting region is formed.

[0095] When manufacturing a light-emitting display device in which the light-emitting layer has three types of light-emitting regions with different light-emitting colors (first light-emitting region, second light-emitting region, and third light-emitting region), first, the first light-emitting region is formed on the functional layer by the first to fourth steps. Next, in order to form the second light-emitting region, the first to fourth steps are repeated on the functional layer in which the first light-emitting region was formed (the first set in the fifth step). In this way, the second light-emitting region is formed on the functional layer in which the first light-emitting region was formed. Next, in order to form the third light-emitting region, the first to fourth steps are repeated on the functional layer in which the first and second light-emitting regions were formed (the second set in the fifth step). In this way, the third light-emitting region is formed on the functional layer in which the first and second light-emitting regions were formed.

[0096] In this case, the light-emitting region may have poor heat resistance. When forming a second light-emitting region on a functional layer on which the first light-emitting region has been formed by performing the first to fourth steps, using the positive-type photosensitive resin composition of the present invention allows for the formation of a solvent-resistant cured film at a relatively low temperature. Therefore, the thermal load on the first light-emitting region can be reduced, and as a result, degradation of the light-emitting region due to heat during the manufacturing of light-emitting display devices can be prevented.

[0097] When forming a second light-emitting region, ensure that the second light-emitting region is not formed on top of the first light-emitting region. When forming a third light-emitting region, ensure that the third light-emitting region is not formed on top of the first and second light-emitting regions.

[0098] The sizes of the first, second, and third light-emitting regions may be the same or different.

[0099] The fifth step allows for the formation of all necessary types of light-emitting regions on the functional layer.

[0100] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0101] [Abbreviations used in the examples] The meanings of the abbreviations used in the following examples are as follows:

[0102] <Polyester Raw Materials> BPADA: 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride ODPA: 4,4'-oxydiphthalic anhydride CBDA: Cyclohexanetetracarboxylic dianhydride TDA: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride DEG: Diethylene glycol BG: 1,4-Butylene glycol IPBPE: 4,4'-isopropylidene bis(2-phenoxyethanol) BHEB: 1,3-bis(2-hydroxyethoxy)benzene PE: 2-phenoxyethanol PA: Phthalic anhydride

[0103] <Catalyst> BTEAC: Benzyltriethylammonium chloride

[0104] <Acrylic copolymer raw materials> MAA: Methacrylic acid MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate CHMI: N-Cyclohexyl maleimide AIBN: Azobisisobutyronitrile

[0105] <Vinyl ether compounds> PVE1: Tris(4-(vinyloxy)butyl) trimellitate PVE2: Bis(4-(vinyloxy)butyl) isophthalate PVE3: 1,4-cyclohexanedimethanol divinyl ether

[0106] <Epoxy Compound> ELM-434: N,N,N',N'-Tetraglycidyl-4,4'-Diaminodiphenylmethane (Trade name: SumiEpoxy ELM-434, manufactured by Sumitomo Chemical Co., Ltd.)

[0107] <Photoacid Generator> PAG1: Irgacure PAG103 (Trade Name) (Manufactured by BASF Japan Ltd.)

[0108] <Surfactant> EFS-521: EFS-521 (product name) (manufactured by DIC Corporation)

[0109] <Solvents> PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether EL: L-(-)-ethyl lactate

[0110] <Hole transport layer> TFB: Poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'(N-(4-sec-butylphenyl)diphenylamine)]

[0111] The number-average molecular weight and weight-average molecular weight of polyesters, polyimide precursors, and acrylic copolymers obtained according to the following synthesis examples were measured using a GPC instrument manufactured by JASCO Corporation (Shodex® columns KF803L and KF804L) under the condition that tetrahydrofuran, the elution solvent, was flowed through the column at a flow rate of 1 ml / min (column temperature 40°C). The number-average molecular weight (hereinafter referred to as Mn) and weight-average molecular weight (hereinafter referred to as Mw) below are expressed as polystyrene equivalent values.

[0112] <Synthesis Example 1> BPADA (122.9 g, 236.2 mmol) and PGMEA (280.0 g) were added to a flask and stirred at room temperature. Then, BTEAC (1.26 g, 5.51 mmol, 1 mol%) was added to the flask. Next, a mixture of DEG (23.82 g, 224.5 mmol, 0.95 eq), PE (3.26 g, 23.62 mmol, 0.1 eq), and PGMEA (70.00 g) was added to the flask and stirred at 100°C for 24 hours to obtain polyester solution [P1] (solid content concentration: 30.0 mass%). The obtained polyester P1 had a Mn of 1,820 and a Mw of 2,730.

[0113] <Synthesis Example 2> BPADA (24.11 g, 46.3 mmol), PA (0.72 g, 4.88 mmol, 0.1 eq), and PGMEA (56.04 g) were added to a flask and stirred at room temperature. Then, BTEAC (0.26 g, 1.14 mmol, 1 mol%) was added to the flask. Next, a mixture of DEG (5.17 g, 48.75 mmol, 0.95 eq) and PGMEA (14.00 g) was added to the flask and stirred at 120°C for 24 hours to obtain polyester solution [P2] (solid content concentration: 30.0 mass%). The obtained polyester P2 had a Mn of 1,750 and a Mw of 2,420.

[0114] <Synthesis Example 3> ODPA (10.48 g, 33.79 mmol) and PGMEA (17.51 ​​g) were added to a flask and stirred at room temperature. Then, BTEAC (0.11 g, 0.47 mmol, 0.6 mol%) was added to the flask. Next, a mixture of DEG (3.59 g, 33.79 mmol, 1.0 eq), PE (0.94 g, 6.76 mmol, 0.2 eq), and PGMEA (17.50 g) was added to the flask and stirred at 120°C for 24 hours to obtain polyester solution [P3] (solid content concentration: 30.0 mass%). The obtained polyester P3 had a Mn of 1,600 and a Mw of 1,890.

[0115] <Synthesis Example 4> BPADA (7.56 g, 14.52 mmol) and PGMEA (10.50 g) were added to a flask and stirred at room temperature. Then, BTEAC (0.08 g, 0.34 mmol, 1 mol%) was added to the flask. Next, a mixture of BG (1.25 g, 13.79 mmol, 0.95 eq), PE (0.20 g, 1.45 mmol, 0.1 eq), and PGMEA (10.50 g) was added to the flask and stirred at 120°C for 24 hours to obtain polyester solution [P4] (solid content concentration: 30.0 mass%). The obtained polyester P4 had a Mn of 1,300 and a Mw of 2,110.

[0116] <Synthesis Example 5> CBDA (5.76 g, 29.38 mmol) and PGMEA (28.00 g) were added to a flask and stirred at room temperature. Then, BTEAC (0.07 g, 0.29 mmol, 1 mol%) was added to the flask. Subsequently, a mixture of IPBPE (8.83 g, 27.91 mmol, 0.95 eq), PE (0.41 g, 2.94 mmol, 0.1 eq), and PGMEA (7.00 g) was added to the flask and stirred at 100°C for 24 hours, and the mixture was reacted at 100°C for 24 hours to obtain polyester solution [P5] (solid content concentration: 30.0 mass%). The obtained polyester P5 had a Mn of 3,930 and a Mw of 8,070.

[0117] <Synthesis Example 6> TDA (8.97 g, 29.86 mmol) and PGMEA (28.00 g) were added to a flask and stirred at room temperature. Then, BTEAC (0.07 g, 0.30 mmol, 1 mol%) was added to the flask. Subsequently, a mixture of BHEB (5.62 g, 28.36 mmol, 0.95 eq), PE (0.41 g, 2.99 mmol, 0.1 eq), and PGMEA (7.00 g) was added to the flask and stirred at 100°C for 24 hours, and the mixture was reacted at 100°C for 24 hours to obtain a polyester solution [P6] (solid content concentration: 30.0 mass%). The obtained polyester P6 had a Mn of 1,750 and a Mw of 2,410.

[0118] <Synthesis Example 7> MAA (15.5 g, 180.0 mmol), CHMI (35.3 g, 197.0 mmol), HEMA (25.5 g, 196.0 mmol), and MMA (23.7 g, 236.7 mmol) were used as monomer components, and AIBN (5.0 g, 30.5 mmol) was used as a radical polymerization initiator. These were polymerized in the solvent PGMEA (195.00 g) at a temperature of 90°C to obtain an acrylic copolymer solution [P7] (solid content concentration: 35.0 mass%). The obtained acrylic copolymer P7 had a Mn of 3,700 and a Mw of 7,200.

[0119] Table 1 below shows the molecular weights of the monomers used in Synthesis Examples 1 to 7 and the resulting polymers.

[0120]

[0121] <Example 1> A positive-type photosensitive resin composition was prepared by adding 1.30 g of PVE1, 0.07 g of PAG1, 0.0045 g of EFS-521, 7.80 g of PGME, and 0.40 g of PGMEA to 5.43 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0122] <Example 2> A positive-type photosensitive resin composition was prepared by adding 1.21 g of PVE1, 0.07 g of PAG1, 0.0045 g of EFS-521, 7.80 g of PGME, and 0.18 g of PGMEA to 5.74 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0123] <Example 3> A positive-type photosensitive resin composition was prepared by adding 1.10 g of PVE1, 0.07 g of PAG1, 0.0045 g of EFS-521, 7.20 g of PGME, and 0.54 g of PGMEA to 6.09 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0124] <Example 4> A positive-type photosensitive resin composition was prepared by adding 0.83 g of PVE1, 0.08 g of PAG1, 0.0045 g of EFS-521, 6.60 g of PGME, and 0.55 g of PGMEA to 6.93 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0125] <Example 5> A positive-type photosensitive resin composition was prepared by adding 1.33 g of PVE1, 0.09 g of PAG1, 0.0045 g of EFS-521, 7.80 g of PGME, and 0.54 g of PGMEA to 5.23 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0126] <Example 6> A positive-type photosensitive resin composition was prepared by adding 0.86 g of PVE2, 0.06 g of PAG1, 0.0030 g of EFS-521, 5.20 g of PGME, and 0.30 g of PGMEA to 3.58 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0127] <Example 7> A positive-type photosensitive resin composition was prepared by adding 1.21 g of PVE3, 0.07 g of PAG1, 0.0045 g of EFS-521, 6.00 g of PGME, and 1.98 g of PGMEA to 5.74 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0128] <Example 8> A positive-type photosensitive resin composition was prepared by adding 0.86 g of PVE1, 0.07 g of PAG1, 5.20 g of PGME, and 0.29 g of PGMEA to 3.58 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0129] <Example 9> A positive-type photosensitive resin composition was prepared by adding 0.89 g of PVE1, 0.06 g of PAG1, 0.0030 g of EFS-521, 5.20 g of PGME, and 0.36 g of PGMEA to 3.49 g of polyester solution [P2] and stirring at room temperature for 30 minutes.

[0130] <Example 10> A positive-type photosensitive resin composition was prepared by adding 0.86 g of PVE1, 0.06 g of PAG1, 0.0030 g of EFS-521, 5.20 g of PGME, and 0.30 g of PGMEA to 3.58 g of polyester solution [P3] and stirring at room temperature for 30 minutes.

[0131] <Example 11> A positive-type photosensitive resin composition was prepared by adding 0.86 g of PVE1, 0.06 g of PAG1, 0.0030 g of EFS-521, 5.20 g of PGME, and 0.30 g of PGMEA to 3.58 g of polyester solution [P4] and stirring at room temperature for 30 minutes.

[0132] <Example 12> A positive-type photosensitive resin composition was prepared by adding 0.89 g of PVE1, 0.06 g of PAG1, 0.0030 g of EFS-521, 5.20 g of PGME, and 0.36 g of PGMEA to 3.49 g of polyester solution [P5] and stirring at room temperature for 30 minutes.

[0133] <Example 13> A positive-type photosensitive resin composition was prepared by adding 0.89 g of PVE1, 0.06 g of PAG1, 0.0030 g of EFS-521, 5.20 g of PGME, and 0.36 g of PGMEA to 3.49 g of polyester solution [P6] and stirring at room temperature for 30 minutes.

[0134] <Comparative Example 1> A positive-type photosensitive resin composition was prepared by adding 0.74 g of PVE1, 0.13 g of PAG1, 0.0045 g of EFS-521, 6.60 g of PGME, and 0.44 g of PGMEA to 7.08 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0135] <Comparative Example 2> A positive-type photosensitive resin composition was prepared by adding 1.39 g of PVE1, 0.06 g of PAG1, 0.0045 g of EFS-521, 7.80 g of PGME, and 0.60 g of PGMEA to 5.15 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0136] <Comparative Example 3> A positive-type photosensitive resin composition was prepared by adding 0.64 g of ELM-434, 0.08 g of PAG1, 0.0030 g of EFS-521, 4.40 g of PGME, and 0.61 g of PGMEA to 4.27 g of polyester solution [P1] and stirring at room temperature for 30 minutes.

[0137] <Comparative Example 4> A positive-type photosensitive resin composition was prepared by adding 0.82 g of PVE1, 0.12 g of PAG1, 0.0045 g of EFS-521, and 8.92 g of PGMEA to 5.13 g of acrylic copolymer solution [P7] and stirring at room temperature for 30 minutes.

[0138] The masses of components (A) to (E) used in Examples 1 to 13 and Comparative Examples 1 to 4 are shown in Table X below.

[0139] In Table 2, (B) / (A) indicates the mass ratio (%) of component (B) to 100 parts by mass of component (A). Note that in Comparative Example 3 in Table 2, ELM-434 is listed in the column for component (B), but ELM-434 is an epoxy compound and not a vinyl ether compound as component (B). Also, in Comparative Example 4 in Table 2, the acrylic copolymer solution [P7] is listed in the column for component (A), but the acrylic copolymer in the acrylic copolymer solution [P7] is not polyester as component (A).

[0140] [Evaluation of Solvent Resistance] Each positive-type photosensitive resin composition from Examples 1 to 13 and Comparative Examples 1 to 4 was applied to a silicon wafer using a spin coater, and then baked on a hot plate at 100°C for 60 seconds to form a coating film (cured film) with a thickness of 1.0 μm. The film thickness was measured using a FILMETRICS F20. This cured film was immersed in PGME, PGMEA, or EL for 60 seconds, and then dried at 100°C for 60 seconds, and the film thickness was measured. A residual film rate of 90% or more after immersion in PGME, PGMEA, or EL was marked as "○", and a rate of less than 90% was marked as "×". The residual film rate was calculated using the following formula: Residual film rate (%) = [B / A] × 100 A: Film thickness before solvent immersion B: Film thickness after solvent immersion

[0141] [Evaluation of Adhesion] <Examples 1-13 and Comparative Examples 1-4> A Xylene solution of TFB (solid content concentration: 1.5% by mass), which is the hole transport layer (hereinafter referred to as HTL), was applied to an ITO-coated glass substrate using a spin coater. The substrate was then baked on a hot plate at 200°C for 30 minutes to form a coating film with a thickness of 40 nm, and an HTL-coated substrate was obtained. The film thickness was measured using a FILMETRICS F20. Each of the positive-type photosensitive resin compositions from Examples 1-13 and Comparative Examples 1-4 was applied to this HTL-coated substrate using a spin coater. The substrate was then baked on a hot plate at 100°C for 60 seconds to form a coating film (cured film) with a thickness of 1.0 μm. The film thickness was measured using a FILMETRICS F20. The cured film was then exposed to light at 365 nm with a Canon UV irradiation device PLA-600FA at a light intensity of 5.5 mW / cm². ２Ultraviolet light was irradiated through a mask having a pattern of rectangular dots measuring 80 μm × 100 μm at the exposure levels listed in Table 3. Next, post-exposure heating (PEB) was performed on a hot plate at 100°C for 60 seconds. Afterward, development was performed by immersion in a 2.38 mass% TMAH aqueous solution for 60 seconds. Following this, the material was washed with ultrapure water for 30 seconds. The formed pattern was observed using an optical microscope. Nichiban tape (CT405AP18) [adhesion strength: 3.93 N / 10 mm] was applied to the formed pattern and then peeled off. The number of peeled dots from the total of 170 formed dots was observed using an optical microscope. Peeling rates of less than 1% were marked "◎", 1% to less than 5% were marked "〇", 5% to less than 10% were marked "△", and 10% or more were marked "×". The peeling rate was calculated using the following formula. Peel rate (%) = [B / A] × 100 A: Total number of patterns before testing B: Number of peeled patterns after testing

[0142] The evaluation results for solvent resistance and adhesion for Examples 1 to 13 and Comparative Examples 1 to 4 are shown in Table 3 below.

[0143]

[0144] As can be seen from the results shown in Table 3, all of Examples 1 to 13 showed high solvent resistance to PGME, PGMEA, or EL, and the films hardened even with low-temperature, short-time firing at 100°C for 1 minute. Furthermore, the formed patterns showed little peeling in adhesion evaluation tests and had excellent HTL adhesion.

[0145] Comparative Example 1 showed high solvent resistance to PGME, PGMEA, or EL, but the pattern peeled off during development, indicating low HTL adhesion. In Comparative Examples 2 to 4, firing at 100°C for 1 minute resulted in the film dissolving upon immersion in PGME, PGMEA, or EL, while low-temperature, short-time firing did not harden the film, indicating insufficient solvent resistance.

[0146] 1. Substrate 1' Substrate 2. Electrode 2' Electrode 3. Hole injection layer 3' Electron injection layer 4. Hole transport layer 4' Electron transport layer 5. Light-emitting layer 5' Light-emitting layer 6. Electron transport layer 6' Hole transport layer 7. Electron injection layer 7' Hole injection layer 8. Upper electrode 8' Upper electrode 9. EL laminate 9' EL laminate 10. Light-emitting display device

Claims

A positive-type photosensitive resin composition containing the following component (A), the following component (B) in an amount of 35.0 parts by mass or more and less than 90.0 parts by mass per 100 parts by mass of the following component (A), the following component (C), and the following component (D). 　 (A) Component: Polyester containing structural units represented by the following formula (1) (B) Component: A vinyl ether compound represented by the following formula (2) or formula (3). (C) Ingredient: Photoacid generator (D) Component: Solvent (In formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group.) (In equation (2), k represents an integer from 1 to 10, and m1 represents an integer from 2 to 6.) In equation (3), m² represents an integer between 2 and 10. 　 The positive-type photosensitive resin composition according to claim 1, wherein the component (A) is obtained by reacting a reaction material containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol represented by the following formula (ii). (In formula (i), X represents a tetravalent organic group. In formula (ii), Y represents a divalent organic group.) 　 The aforementioned X represents a tetravalent organic group represented by any of the following formulas (X-1) to (X-16): The aforementioned Y represents a divalent organic group represented by any of the following formulas (Y-1) to (Y-10): The positive-type photosensitive resin composition according to claim 1. (In the formula, n1 represents an integer from 1 to 4. n2 represents an integer from 1 to 7. * represents a combination.) 　 The positive-type photosensitive resin composition according to claim 1, wherein the component (A) has an end group represented by the following formula (E1) or formula (E2). (In formula (E1), R １ * represents a monovalent organic residue obtained by removing the hydroxyl group from a monoalcohol. * represents a bond. In formula (E2), R ２ represents a divalent organic residue obtained by removing the acid anhydride structure from a dicarboxylic acid anhydride. * represents a bond. 　 The positive-type photosensitive resin composition according to claim 1, wherein the weight-average molecular weight of component (A) is 1,000 or more and 30,000 or less. 　 The positive-type photosensitive resin composition according to claim 1, wherein the content of component (C) is 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of component (A). 　 The positive-type photosensitive resin composition according to claim 1, further comprising the following component (E). 　 (E) Ingredient: Surfactant A positive-type photosensitive resin composition according to claim 1, used in the manufacture of a light-emitting display device. 　 A step of applying a positive-type photosensitive resin composition according to any one of claims 1 to 8 onto a functional layer, then heating to form a cured photosensitive resin layer, The process involves exposing the cured photosensitive resin layer to light through a photomask and developing it to form a patterned photosensitive resin layer having openings. A step of forming a light-emitting region on the exposed functional layer within the opening of the patterned photosensitive resin layer, A method for manufacturing an luminescent display device, including the following. 　 The method for manufacturing a light-emitting display device according to claim 9, wherein the light-emitting region includes quantum dots.

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