Photosensitive composition, cured product, and organic EL display device

Abstract

A purpose of the present invention is to provide a photosensitive composition which has high light-shielding properties and sensitivity and from which a pattern having excellent linearity and having little residue around the pattern edges can be formed in accordance with mask dimensions. The resultant cured object, when used in an organic-EL display device, makes the display device have few non-luminescent pixels therein.　This photosensitive composition comprises all of the following components (a)-(d), and the solid components in the photosensitive composition have a double bond equivalent of 1,000-3,500 g / mol. Component (a): A black pigment Component (b): An alkali-soluble resin Component (c): A radical-polymerizable compound Component (d): A photopolymerization initiator

Description

[Technical Field]

[0001] The present invention relates to a photosensitive composition, a cured product, and a display device for organic EL. [Background technology]

[0002] In recent years, many products using organic electroluminescent (EL) display devices have been developed for thin-screen displays such as smartphones, tablet PCs, and televisions.

[0003] Generally, organic EL display devices have a transparent electrode made of indium tin oxide (hereinafter referred to as "ITO") on the light-extracting side of the light-emitting element, and a metal electrode made of a magnesium-silver alloy on the side of the light-emitting element that does not extract light. In addition, an insulating layer called a pixel-splitting layer is formed between the layers of the transparent electrode and the metal electrode to separate the pixels of the light-emitting element.

[0004] In recent years, attempts have been made to improve the visibility and contrast of organic EL display devices by imparting light-shielding properties to the pixel division layer, thereby reducing the reflection of external light such as sunlight. As a specific example, a negative-type black photosensitive resin composition using a black pigment has been disclosed (see, for example, Patent Documents 1 and 2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 2018 / 061525 [Patent Document 2] International Publication No. 2018 / 101314 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, when patterning photosensitive compositions such as those described in Patent Documents 1 and 2 with a high-concentration alkaline developer, it is necessary to over-photocure the exposed areas in order to improve their resistance to the alkaline developer. As a result, there are problems such as residue formation at the pattern edges and deterioration of pattern linearity. Furthermore, in the case of hole pattern processing of 10 μm or less, which is required for high-definition display applications in particular, the absolute value of the difference between the mask design width and the hole pattern formation width (hereinafter sometimes referred to as mask bias) becomes too large, making it difficult to form the desired pattern.

[0007] Furthermore, in negative-type photosensitive compositions such as those described in Patent Document 2, the alkali-soluble resin does not have an amine value, making it impossible to reduce the particle size of the black pigment. When used in an organic EL display device using the cured product, the electrode wiring can short-circuit starting from the coarse pigment, resulting in the problem of certain pixels not lighting up. [Means for solving the problem]

[0008] To solve the above problems, the present invention has the following configuration. That is, (1) A photosensitive composition containing all of the following components (a) to (d), wherein the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500 g / mol. (a) Ingredients: Black pigment (b) Components: Alkali-soluble resin (c) Component: Radical polymerizable compound (d) Component: Photopolymerization initiator (2) The photosensitive composition according to (1) above, wherein the component (c) comprises the component (c-1) described below. (c-1) Component: A radical polymerizable compound having two ethylenically unsaturated bonds in its molecule and a double bond equivalent of 200-600 g / mol. (3) The photosensitive composition according to (2) above, wherein the content of component (c-1) is 60 to 100% by weight of component (c). (4) The photosensitive composition according to any one of (1) to (3) above, wherein the component (b) contains the component (b-1) described below. (Component (b-1): An alkali-soluble resin having an amine value of 2.0 to 10.0 mgKOH / g) (5) The photosensitive composition according to (4) above, wherein the component (b-1) has a structural unit represented by formula (1) and / or a structural unit represented by formula (2) and a structural unit represented by formula (3).

[0009] [Chemical formula]

[0010] [Chemical formula] [[ID=,20]]

[0011] [Chemical formula]

[0012] (In formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a divalent alkyleneoxyalkylene group having 2 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 3 and R 4 each independently represent any one selected from an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms. In formula (2), R 5 represents a hydrogen atom or a methyl group, R 6 represents any one selected from an alkylene group having 1 to 4 carbon atoms, a divalent alkyleneoxyalkylene group having 2 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R 7 , R 8 and R 9Each of the following is independently selected from alkyl groups having 1 to 4 carbon atoms, alkoxyalkyl groups having 2 to 4 carbon atoms, alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and aromatic hydrocarbon groups having 6 to 10 carbon atoms, while X represents one of the following: a bromine atom, a chlorine atom, an iodine atom, a bisulfate, or a hydroxide. In formula (3), R 10 and R 11 Each is independently a hydrogen atom or a methyl group, R 12 (This represents one of the following: an alkylene group with 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 6 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 10 carbon atoms.) (6) The photosensitive composition according to any one of (1) to (5) above, wherein the component (b) contains the component (b-2) described below. (b-2) Components: A resin that does not have the structural unit represented by formula (1) or the structural unit represented by formula (2), and has a hydroxyl value of 60 mgKOH / g or more. (7) A compound containing the above-mentioned component (b-1) and component (b-2), wherein the weight ratio W of component (b-1) to component (b-2) b-1 / W b-2 The photosensitive composition described in (6) above, wherein the ratio is 0.2 to 1.5. (8) The photosensitive composition according to any one of (1) to (7) above, wherein the component (d) contains an oxime ester-based photopolymerization initiator having a fluorine atom in the molecule. (9) The photosensitive composition according to any one of (1) to (8) above, wherein the component (a) contains at least one compound selected from the group consisting of a compound represented by formula (4), a compound represented by formula (5), and isomers thereof.

[0013] [ka]

[0014] (In equations (4) and (5), R 13 and R 18 Each of these independently represents a hydrogen atom, CH3, CF3, or fluorine atom. 14 , R 15 , R 16 , R 17 , R19 , R 20 , R 21 and R 22 These are, independently, a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C1-C12 cycloalkyl group, a C1-C12 alkenyl group, a C1-C12 cycloalkenyl group, a C1-C12 alkynyl group, COOH, COOR 23 COO - CONH2, CONHR 23 CONR 23 R 24 , CN, OH, OR 23 OCOR 23 OCONH2, OCONHR 23 OCONR 23 R 24 Represents R 23 and R 24 Each of these independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, or an alkynyl group having 1 to 12 carbon atoms. (10) The photosensitive composition according to any one of (1) to (9) above, wherein the 50% cumulative diameter in the volume-based particle size distribution of the particulate components in the photosensitive composition, as measured by dynamic light scattering, is 20 to 60 nm. (11) The photosensitive composition according to any of (1) to (10) above, further comprising the component (e) below. (e) Ingredients: Silica particles (12) The photosensitive composition according to (11) above, wherein the average primary particle size of component (e) is 10 to 30 nm. (13) A component containing the (b-1) component, with a weight ratio W of the (e) component to the (b-1) component. e / W b-1 A photosensitive composition according to (11) or (12) above, wherein the ratio is 0.5 to 2.0. (14) A component containing the (b-2) component, with a weight ratio W of the (e) component to the (b-2) component. e / W b-2 A photosensitive composition according to any of (11) to (13) above, wherein the ratio is 0.15 to 1.0. (15) A cured product obtained by curing any of the photosensitive compositions described in (1) to (14) above. (16) An organic EL display device comprising the cured product described in (15) above. [Effects of the Invention]

[0015] According to the photosensitive composition of the present invention, it is possible to obtain a photosensitive composition that has high light-shielding properties and sensitivity, while having little residue at the pattern edges, allowing for the formation of a pattern with excellent linearity according to the mask dimensions, and resulting in fewer unlit pixels when the cured product is used in an organic EL display device. [Brief explanation of the drawing]

[0016] [Figure 1] This is a schematic diagram of the fabrication procedure for the organic EL display device in the example. [Modes for carrying out the invention]

[0017] The photosensitive composition of the present invention is a photosensitive composition containing all of the following components (a) to (d), wherein the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500 g / mol. (a) Ingredients: Black pigment (b) Components: Alkali-soluble resin (c) Component: Radical polymerizable compound (d) Component: Photopolymerization initiator.

[0018] The photosensitive composition of the present invention contains (a) component: black pigment. (a) Components: In black pigments, "black" refers to those whose Color Index Generic Number (hereinafter, "CI number") includes "BLACK". In the case of mixtures or those without a CI number, it refers to those that are black when cured. The term "black when cured" means that, in the transmission spectrum of the cured product of a composition containing component (a), when the transmittance per 1.0 μm of film thickness at a wavelength of 550 nm is converted using the Lambert-Beer formula within the range of 0.1 to 1.5 μm so that the transmittance at a wavelength of 550 nm is 10%, the transmittance in the converted transmission spectrum at wavelengths of 450 to 650 nm is 25% or less. (a) As components, black organic pigments and black inorganic pigments can be used. Examples of black organic pigments include perylene black, aniline black, or benzofuranone pigment (as described in Japanese Patent Publication No. 2012-515233). Examples of black inorganic pigments include carbon black, titanium nitride, titanium oxynitride, titanium carbide, zirconium nitride, zirconium oxynitride, and black iron oxide.

[0019] By combining these black pigments, a photosensitive composition with desired optical properties can be obtained. Component (a) preferably contains a benzofuranone pigment from the viewpoint of visible light shielding and insulating properties per unit weight.

[0020] In the photosensitive composition of the present invention, it is preferable that component (a) contains at least one compound selected from the group consisting of compounds represented by formula (4), compounds represented by formula (5), and isomers thereof.

[0021] [ka]

[0022] In equations (4) and (5), R 13 and R 18 Each of these independently represents a hydrogen atom, CH3, CF3, or fluorine atom.14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 21 and R 22 These are, independently, a hydrogen atom, a halogen atom, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C2-C12 alkenyl group, a C3-C12 cycloalkenyl group, a C2-C12 alkynyl group, COOH, and COOR. 23 COO - CONH2, CONHR 23 CONR 23 R 24 , CN, OH, OR 23 OCOR 23 OCONH2, OCONHR 23 OCONR 23 R 24 Represents R 23 and R 24 Each of these independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. The compounds represented by formula (4), the compounds represented by formula (5), and their isomers are all benzofuranone pigments.

[0023] From the viewpoint of light-shielding properties per unit film thickness, the content of component (a) in the photosensitive composition is preferably 5% by weight or more, and more preferably 10% by weight or more, based on 100% by weight of the solid content of the photosensitive composition. On the other hand, from the viewpoint of improving sensitivity during exposure and fine line processing properties, the content of component (a) is preferably 50% by weight or less, and more preferably 40% by weight or less, based on 100% by weight of the photosensitive composition.

[0024] In this invention, the term "solid content" refers to components other than the organic solvent in the photosensitive composition.

[0025] The photosensitive composition of the present invention contains (b) component: alkali-soluble resin. Examples of component (b) include epoxy resins, acrylic resins, phenolic resins, siloxane polymer resins, or polyimide resins. Among these, it is preferable that component (b) contains an acrylic resin from the viewpoint of excellent storage stability and photosensitive properties of the photosensitive composition.

[0026] As the acrylic resin, a carboxyl group-containing acrylic resin is preferred. As the carboxyl group-containing acrylic resin, a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferred. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, or vinyl acetic acid. These may be used alone or in combination with copolymerizable ethylenically unsaturated compounds.

[0027] Examples of copolymerizable ethylenically unsaturated compounds include unsaturated carboxylate alkyl esters such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, benzyl acrylate or benzyl methacrylate, styrene, p-methylstyrene, o-methylstyrene, m-methyl Examples include aromatic vinyl compounds such as styrene or α-methylstyrene, unsaturated carboxylic acid aminoalkyl esters such as aminoethyl acrylate, unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate or glycidyl methacrylate, vinyl carboxylic acid esters such as vinyl acetate or vinyl propionate, vinyl cyanide compounds such as acrylonitrile, methacrylonitrile or α-chloroacrylonitrile, aliphatic conjugated dienes such as 1,3-butadiene or isoprene, and polystyrene, polymethyl acrylate, polymethyl methacrylate, polybutyl acrylate or polybutyl methacrylate, each having an acryloyl group or methacryloyl group at its terminus. From the viewpoint of solubility in alkaline developer, it is preferable that component (b) is a 2- to 4 copolymer having a structure obtained by copolymerizing an unsaturated carboxylic acid or ethylenically unsaturated compound selected from the group consisting of methacrylic acid, acrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate and styrene, and containing an acrylic resin with an acid value of 70 to 150 (mgKOH / g). By selecting an appropriate ethylenically unsaturated compound and forming a 2- to 4-component copolymer, heat resistance and solvent solubility can be further improved. Furthermore, by setting the acid value within this range, it becomes easier to achieve an appropriate dissolution rate in high-concentration alkaline developers.

[0028] The weight-average molecular weight (Mw) of component (b) is preferably 2,000 to 100,000, and more preferably 10,000 to 50,000. This range makes it easier to adjust the dissolution rate of component (b) in the alkaline developer to an appropriate range, and facilitates the formation of low-taper angle shapes by controlling the reflowability during thermal curing. The weight-average molecular weight (Mw) is determined by measuring the weight-average molecular weight (Mw) in terms of polystyrene using a GPC analyzer. Specifically, the weight-average molecular weight of component (b) is measured under the following conditions. Measuring device: Waters 2695 (manufactured by Waters) Column temperature: 50℃ Flow rate: 0.4mL / min Detector: 2489 UV / Vis Detector (Measurement wavelength 260nm) Developing solvent: NMP (containing 0.21% lithium chloride and 0.48% phosphoric acid by weight) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation) Number of measurements: 2 (the average value is taken as the weight-average molecular weight of component (b)).

[0029] Furthermore, it is preferable that component (b) contains an acrylic resin having an ethylenically unsaturated group in its side chain. Including such an acrylic resin tends to improve sensitivity during exposure and development. As the ethylenically unsaturated group, an acrylic group or a methacrylic group is preferred. Such an acrylic resin can be obtained, for example, by adding an ethylenically unsaturated compound having a glycidyl group or an alicyclic epoxy group to the carboxyl group of an acrylic (co)polymer having a carboxyl group.

[0030] In the photosensitive composition of the present invention, it is preferable that component (b) contains the following component (b-1). (b-1) Components: Alkali-soluble resin with an amine value of 2.0 to 10.0 mg KOH / g (b-1) Setting the amine value of component (b-1) to 2.0 mg KOH / g or higher makes it easier to inhibit dissolution in high-concentration alkaline developers, improving the processability of fine patterns. Setting the amine value of component (b-1) to 10.0 mg KOH / g or lower improves its affinity with developers, making it easier for unexposed areas to dissolve uniformly even in high-concentration developers that do not contain surfactants, and as a result, it becomes easier to obtain cured products with excellent pattern linearity.

[0031] In the photosensitive composition of the present invention, it is preferable that the (b-1) component has a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (3).

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] In formula (1), R 1 R is a hydrogen atom or a methyl group. 2 R is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alkylene oxyalkylene group having 2 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. 3 and R 4 Each of these independently represents one of the following: an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

[0036] The structural unit represented by formula (1) is a (meth)acrylic unit having a tertiary amino group. Examples of such (meth)acrylic units include, but are not particularly limited to, (meth)acrylic units that can be obtained by polymerizing 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dipropylaminoethyl acrylate, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2-dipropylaminoethyl methacrylate, 2-diphenylaminoethyl methacrylate, and 2-benzylaminoethyl methacrylate. These (meth)acrylic units may be included individually or in combination of two or more types.

[0037] The structural unit represented by formula (1) can be introduced, for example, by copolymerizing an unsaturated monomer having a tertiary amino group.

[0038] In formula (2), R 5 R is a hydrogen atom or a methyl group. 6 R is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alkylene oxyalkylene group having 2 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms. 7 , R 8 and R 9 Each of the following is independently selected from alkyl groups having 1 to 4 carbon atoms, alkoxyalkyl groups having 2 to 4 carbon atoms, alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and aromatic hydrocarbon groups having 6 to 10 carbon atoms, while X represents one of the following: a bromine atom, a chlorine atom, an iodine atom, a bisulfate, or a hydroxide.

[0039] The structural unit represented by formula (2) is a (meth)acrylic unit having a quaternary ammonium salt. Examples of such (meth)acrylic units include, but are not limited to, (meth)acrylic units that can be obtained by polymerizing dimethylaminoethylmethyl chloride acrylate, dimethylaminoethylbenzyl chloride acrylate, dimethylaminoethylmethyl methacrylate, dimethylaminoethylbenzyl chloride methacrylate, etc. These (meth)acrylic units may be included individually or in groups of two or more.

[0040] The structural unit represented by formula (2) can be introduced, for example, by copolymerizing an unsaturated monomer having a quaternary ammonium salt.

[0041] Of the structural units represented by formula (1) and formula (2), from the viewpoint of reducing wiring damage in organic EL display devices and reducing non-illuminated pixels, the molar ratio of the structural unit represented by formula (2) is preferably 50 mol% or less, and more preferably 20 mol% or less, relative to the total of formulas (1) and (2). Furthermore, the structural unit represented by formula (1) is preferably a tertiary amine, and more preferably 2-dimethylaminoethyl methacrylate.

[0042] In formula (3), R 10 and R 11 Each is independently a hydrogen atom or a methyl group, R 12 represents one of the following selected from alkylene groups having 1 to 4 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 10 carbon atoms. Having a structural unit represented by formula (3) makes it easier to improve the exposure sensitivity of the photosensitive composition.

[0043] The method for introducing the structural unit represented by formula (3) is not particularly limited and can be introduced by known methods. For example, one method involves adding a glycidyl group-containing polymerizable unsaturated monomer to a (meth)acrylic copolymer obtained by copolymerizing carboxyl group-containing unsaturated monomers. In this case, examples of carboxyl group-containing unsaturated monomers to be copolymerized include acrylic acid and methacrylic acid. Examples of glycidyl-containing unsaturated monomers include glycidyl acrylate and glycidyl methacrylate.

[0044] In the photosensitive composition of the present invention, it is preferable that component (b) contains the following component (b-2). (b-2) Components: A resin that does not have the structural unit represented by formula (1) or the structural unit represented by formula (2), and has a hydroxyl value of 60 mgKOH / g or more. The hydroxyl value of component (b-2) is 60 mgKOH / g or higher, and more preferably 80 mgKOH / g or higher. Keeping the hydroxyl value within this range improves affinity with the developer, improves linearity of the pattern, and helps suppress residue at the edges. There is no particular upper limit to the hydroxyl value, but it is usually around 450 mgKOH / g. The hydroxyl value is measured as follows: First, component (b-2) is dried in an 80°C vacuum dryer for 10 hours or more to prepare a dried sample. Next, 2 g of the dried sample is dissolved in 5 ml of a 250 g / L pyridine solution of acetic anhydride. After adding 1 ml of water to decompose the acetic anhydride, the hydroxyl value can be calculated by titrating with a 0.5 mol / L potassium hydroxide ethanol solution. If a resin can correspond to either component (b-1) or component (b-2), the resin is considered to be component (b-1).

[0045] Component (b-2) has a hydroxyl group. Preferably, the hydroxyl group of component (b-2) is a phenolic hydroxyl group. The presence of a phenolic hydroxyl group in component (b-2) suppresses excessive radical reactions caused by exposure, thereby reducing mask bias.

[0046] (b-2) Examples of resins containing hydroxyl groups that are component (b-2) include hydroxyl group-containing epoxy acrylate resins, hydroxyl group-containing acrylic resins, phenol resins, hydroxyl group-containing siloxane polymer resins, or hydroxyl group-containing polyimide resins. Among these, phenol resins or hydroxyl group-containing acrylic resins are preferred from the viewpoint of storage stability and pattern processing properties of the photosensitive composition.

[0047] Phenolic resins are resins having phenolic hydroxyl groups, obtained by reacting a phenol compound with an aldehyde compound or a ketone compound, and possess an aromatic structure derived from the phenol compound. If the aldehyde compound and / or ketone compound also has an aromatic structure, the resin also possesses an aromatic structure derived from them. Therefore, by including phenolic resin in a composition, the heat resistance of the resulting cured product can be improved. For this reason, phenolic resins are suitable for applications where heat resistance is required.

[0048] Examples of phenolic compounds include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 4-n-propylphenol, 4-n-butylphenol, 4-t-butylphenol, 1-naphthol, 2-naphthol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, catechol, resorcinol, 1,4-hydroquinone, pyrogallol, 1,2,4-benzenetriol, or phloroglucinol.

[0049] Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, or salicylaldehyde.

[0050] Examples of ketone compounds include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or benzophenone.

[0051] The phenolic resin is preferably a novolac resin obtained by reacting a phenolic compound with an aldehyde compound and / or a ketone compound under acid catalysis. The reaction between the phenolic compound and the aldehyde compound and / or ketone compound can be carried out in a solvent or without a solvent.

[0052] Furthermore, the phenolic resin may be a resol resin, which is obtained by the same reaction except that a base catalyst is used instead of an acid catalyst.

[0053] Examples of acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, or polycarboxylic acids, or their anhydrides, or ion exchange resins. Examples of base catalysts include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, diethylamine, triethanolamine, diethanolamine, N,N-dimethyl-4-aminopyridine, sodium hydroxide, potassium hydroxide, or ion exchange resins.

[0054] A hydroxyl group-containing acrylic resin can be obtained, for example, by a method similar to that used for the aforementioned acrylic resin, using a copolymerizable hydroxyl group-containing or phenolic hydroxyl group-containing ethylenically unsaturated compound.

[0055] Examples of copolymerizable ethylenically unsaturated compounds containing hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, and 6-hydroxyhexyl methacrylate.

[0056] Examples of copolymerizable phenolic hydroxyl group-containing ethylenically unsaturated compounds include 4-hydroxyphenyl methacrylate (PQMA), (4-hydroxyphenyl)methyl methacrylate, (4-hydroxyphenyl)ethyl methacrylate, (4-hydroxyphenyl)propyl methacrylate, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,4-dihydroxystyrene, 2,6-dihydroxystyrene, 2,4,6-trihydroxystyrene, 2,3,4,5-tetrahydroxystyrene, pentahydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 1-(2-hydroxyphenyl)propylene, 1-3-hydroxyphenyl)propylene, or 1-(4-hydroxyphenyl)propylene.

[0057] The photosensitive composition of the present invention contains the above-mentioned component (b-1) and component (b-2), wherein the weight ratio of component (b-1) to component (b-2) is W b-1 / W b-2 It is preferable that it is between 0.2 and 1.5, and more preferably between 0.3 and 1.2. b-1 / W b-2 By setting it to 0.2 or higher, the machinability of fine patterns can be further improved. Also, W b-1 / W b-2 By setting the ratio to 1.5 or less, compatibility with the developer is further improved, and pattern linearity can be further enhanced.

[0058] From the viewpoint of improving sensitivity during exposure, the content of component (b) in the photosensitive composition of the present invention is preferably 60% by weight or less, and more preferably 50% by weight or less, based on 100% by weight of the solid content of the photosensitive composition. Furthermore, from the viewpoint of improving the flexibility of the cured film and reducing cracks, the content of component (b) is preferably 10% by weight or more, and more preferably 20% by weight or more, based on 100% by weight of the solid content of the photosensitive composition.

[0059] From the viewpoint of storage stability of the photosensitive composition, the content of component (b-1) in the photosensitive composition of the present invention is preferably 2% by weight or more, and more preferably 5% by weight or more, based on 100% by weight of the solid content of the photosensitive composition. Furthermore, from the viewpoint of reducing residue at the pattern openings, the content of component (b-1) is preferably 40% by weight or less, and more preferably 30% by weight or less, based on 100% by weight of the solid content of the photosensitive composition.

[0060] From the viewpoint of improving compatibility with the developer and improving pattern linearity, the content of component (b-2) in the photosensitive composition of the present invention is preferably 10% by weight or more, and preferably 20% by weight or more, based on 100% by weight of the solid content of the photosensitive composition. Furthermore, from the viewpoint of improving sensitivity during exposure, the content of component (b-2) is preferably 50% by weight or less, and preferably 40% by weight or less, based on 100% by weight of the solid content of the photosensitive composition.

[0061] The photosensitive composition of the present invention contains (c) component: a radical polymerizable compound. A radical polymerizable compound refers to a component having a radical polymerizable group in its molecule, and a radical polymerizable group refers to a group to which a methyl radical can be added at room temperature, and which generates another radical when a methyl radical is added. A method for generating a methyl radical at room temperature is to irradiate a photopolymerization initiator having an acetyl oxime ester structure with an activating ray (radiation). A method for detecting another radical generated when a methyl radical is added is electron spin resonance analysis. Furthermore, a method for confirming that another radical has been generated when a methyl radical is added is to irradiate a composition obtained by dissolving a compound having a radical polymerizable group and a photopolymerization initiator having an acetyl oxime ester structure in a solvent with an activating ray, and confirm by checking for an increase in viscosity or a change in appearance such as gelation or film formation before and after irradiation with the activating ray. Examples of activating rays include visible light, ultraviolet light, electron beams, or X-rays. It is preferable that the other radical generated when a methyl radical is added to a radical polymerizable group can further be added to another radical polymerizable group. Furthermore, it is preferable that when a methyl radical is added to another radical polymerizable group, another radical is similarly generated. The other radical generated when a methyl radical is added to a radical polymerizable group is preferably a carbon radical, oxygen radical, nitrogen radical, or sulfur radical, with a carbon radical being more preferable. As for the radical polymerizable group of component (c), from the viewpoint of improving sensitivity during exposure, an ethylenically unsaturated bond is preferred, and an acrylic group or a methacrylic group is more preferred. Component (c) may have two or more radical polymerizable groups.

[0062] (c) Component (c) preferably contains a compound having two or more radical polymerizable groups. Examples of such component (c) include bisphenol A diglycidyl ether (meth)acrylate, poly(meth)acrylate carbamate, modified bisphenol A epoxy (meth)acrylate, 1,6-hexanediol adipic acid (meth)acrylate, propylene oxide phthalate anhydride (meth)acrylate, diethylene glycol trimellitic acid (meth)acrylate, rosin-modified epoxy di(meth)acrylate, alkyd-modified (meth)acrylate, and ful Orange acrylate oligomer, tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, triacrylic formal, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate Rate, 2,2-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]propane, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]sulfone, bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]ether, 4,4'-bis[4-(3-acryloxy-2-hydroxypropoxy)phenyl]cyclohexane, 9,9-bis[4-(3-acryloxy- Examples include 2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-methyl-4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3-chloro-4-(3-acryloxy-2-hydroxypropoxy)phenyl]fluorene, bisphenoxyethanol fluororange acrylate, bisphenoxyethanol fluororange methacrylate, biscresol fluororange acrylate, and biscresol fluororange methacrylate. The photosensitive composition may contain two or more of these.

[0063] From the viewpoint of preventing deterioration of mask bias due to excessive photocuring of exposed areas and pattern edges, and suppressing residue in the pattern edges, it is preferable that the photosensitive composition of the present invention contains component (c) as described below. (c-1) Component: A radical polymerizable compound having two ethylenically unsaturated bonds in the molecule and a double bond equivalent of 200-600 g / mol.

[0064] The double bond equivalent of component (c-1) is preferably 200 g / mol or more in order to suppress excessive hardening in the exposed areas and the edges of the exposed pattern, which can lead to the generation of residue at the pattern edges. Furthermore, from the viewpoint of improving fine wire processability and exposure sensitivity, it is preferably 600 g / mol or less, and more preferably 400 g / mol or less.

[0065] The double bond equivalent of a radical polymerizable compound, as used here, refers to the weight of the radical polymerizable compound per mole of ethylenically unsaturated double bond groups. The unit of double bond equivalent is g / mol. The number of ethylenically unsaturated double bond groups in a radical polymerizable compound can be determined from the double bond equivalent value. The double bond equivalent can also be calculated from the iodine value.

[0066] The iodine value referred to here is the amount of halogen that reacts with 100g of sample, converted to the weight of iodine. The unit of iodine value is gI / 100g. It can be determined by reacting 100g of sample with iodine monochloride, capturing unreacted iodine with potassium iodide aqueous solution, and then titrating the unreacted iodine with sodium thiosulfate aqueous solution.

[0067] When the photosensitive composition of the present invention contains component (c-1), it is preferable that the content of component (c-1) is 60 to 100% by weight of component (c). By setting the content of component (c-1) to 60% by weight or more, it becomes easier to suppress excessive hardening of the exposed area and pattern edge portion, and it becomes easier to suppress the generation of edge residue.

[0068] From the viewpoint of improving sensitivity during exposure, the content of component (c) in the photosensitive composition of the present invention is preferably 10% by weight or more, and more preferably 15% by weight or more, of the total content of components (b) and (c) in 100% by weight. On the other hand, from the viewpoint of reflowability in the heating and firing process, the content of component (c) is preferably 80% by weight or less, and more preferably 60% by weight or less, of the total content of components (b) and (c) in 100% by weight.

[0069] In the photosensitive composition of the present invention, the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500 g / mol. By setting the double bond equivalent to 1000 g / mol or more, excessive photocuring during exposure can be suppressed, pattern linearity can be improved, and residue at the pattern edges can be suppressed. Furthermore, by setting the double bond equivalent to 1000 g / mol or more, the hardness and chemical resistance of the cured film can be improved. On the other hand, by setting the double bond equivalent to 3500 g / mol or less, high sensitivity can be maintained even in films with high light-shielding properties. In addition, by setting the double bond equivalent to 3500 g / mol or less, the flexibility of the cured film is improved, making it possible to apply it to foldable organic EL display devices.

[0070] The double bond equivalent of solids referred to here is the weight of solids per mole of ethylenically unsaturated double bond groups. The unit of double bond equivalent of solids is g / mol. From the value of double bond equivalent, the number of ethylenically unsaturated double bond groups in the solids can be determined. Double bond equivalent can be calculated from the iodine value.

[0071] The photosensitive composition of the present invention contains (d) component: a photopolymerization initiator.

[0072] Component (d) refers to a compound that undergoes bond cleavage and / or reaction to generate radicals upon exposure. Examples of component (d) include carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and α-aminoalkylphenone-based photopolymerization initiators. Component (d) may contain two or more of these. In particular, in the exposure process described later, the sensitivity to a mixed line consisting of i-line (365 nm), h-line (405 nm), and g-line (436 nm) is high, so it is preferable that component (d) contains an oxime ester-based photopolymerization initiator.

[0073] Examples of oxime ester-based photopolymerization initiators include 1-phenyl-1,2-butanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-methoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, 1-phenyl-1,2-propanedione-2-(o-benzoyl)oxime, bis(α-isonitrosopropiophenone oxime)isophthal, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(o-benzoyloxime)], IRGACURE (registered trademark, hereinafter the same) OXE01, IRGACURE OXE02 (all trade names, manufactured by BASF Ltd.), N-1818, N-1919, NCI-831 (all trade names, manufactured by ADEKA Corporation), etc.

[0074] In the photosensitive composition of the present invention, it is more preferable that component (d) contains an oxime ester-based photopolymerization initiator having a fluorine atom in the molecule. By having a fluorine atom in the molecule, the hydrophobicity of the coating film can be improved, and the dissolution rate in high-concentration alkaline developers can be slowed down.

[0075] Examples of oxime ester-based photopolymerization initiators containing a fluorine atom in the molecule include the photopolymerization initiator represented by formula (6).

[0076] [ka]

[0077] R 23 R represents a fluoroalkyl group. 23 Examples include the 2,2,3,3-tetrafluoropropyl group, the 2,2,2-trifluoroethyl group, and the 2,2,3,3,4,4,5,5-octafluoropentyl group. Among these, component (d) is R 23 It is preferable that the compound contains IRGACURE OXE03, which is represented by a 2,2,3,3-tetrafluoropropyl group.

[0078] From the viewpoint of improving sensitivity to exposure, the content of component (d) in the photosensitive composition is preferably 1 part by weight or more, and more preferably 5 parts by weight or more, per 100 parts by weight of the total amount of components (b) and (c). On the other hand, from the viewpoint of fine wire processability, the content of component (d) is preferably 60 parts by weight or less, and more preferably 40 parts by weight or less, per 100 parts by weight of the total amount of components (b) and (c).

[0079] The photosensitive composition of the present invention may contain an organic solvent. Examples of organic solvents include ethers, acetates, esters, ketones, aromatic hydrocarbons, amides, and alcohols.

[0080] Examples of ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tetrahydrofuran, and the like.

[0081] Examples of acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA"), propylene glycol monoethyl ether acetate, and dipropylene glycol methyl ether acetate.

[0082] Examples of esters include methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, and the like.

[0083] Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

[0084] Examples of aromatic hydrocarbons include toluene and xylene.

[0085] Examples of amides include N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0086] Examples of alcohols include butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, and diacetone alcohol.

[0087] The photosensitive composition of the present invention may contain two or more of these organic solvents. Furthermore, the boiling point of the organic solvent at 1 atmosphere is preferably 170°C or lower, and more preferably 150°C or lower, because the solvent is likely to volatilize even when low-temperature firing is performed after patterning.

[0088] The photosensitive composition of the present invention may contain a surfactant, if necessary, to improve wettability with the substrate or improve the uniformity of the film thickness of the coating. Commercially available compounds can be used as surfactants. Specifically, examples of silicone-based surfactants include the SH series, SD series, and ST series from Toray Dow Corning Corporation, the BYK series from Bic Chemie Japan, the KP series from Shin-Etsu Silicone Co., Ltd., the Disform series from Nippon Oil & Fats Co., Ltd., and the TSF series from Toshiba Silicone Co., Ltd. Examples of fluorine-based surfactants include the "Megafac®" series from Dainippon Ink & Co., Ltd., the Florard series from Sumitomo 3M Co., Ltd., the "Surflon®" series and "Asahiguard®" series from Asahi Glass Co., Ltd., the EF series from Shin Akita Chemical Co., Ltd., and the Polyfox series from Omnova Solutions Co., Ltd. Examples of surfactants consisting of acrylic and / or methacrylic polymers include the Polyflow series from Kyoeisha Chemical Co., Ltd. and the "Disparon®" series from Kusumoto Chemical Co., Ltd. The surfactants that can be contained in the photosensitive composition of the present invention are not limited to the above examples.

[0089] The photosensitive composition of the present invention may contain a polymeric dispersant. A polymeric dispersant is a substance that has both affinity groups that chemically bond to or adsorb to the surface of the black pigment and polymer chains or groups that are solvent-friendly. Since polymeric dispersants do not have ethylenically unsaturated groups, there is a concern that adding a large amount may worsen the desired photosensitive performance, and it is desirable to add an appropriate amount considering dispersion stability and photosensitive performance. In the wet media dispersion treatment described later, the polymeric dispersant improves the wettability of the black pigment to the dispersion medium, promotes the deaggregation of the black pigment, stabilizes particle size and viscosity due to steric hindrance and / or electrostatic repulsion effects, and further suppresses the occurrence of color separation during storage or coating of the photosensitive composition.

[0090] Examples of polymer dispersants include polyester-based polymer dispersants, acrylic-based polymer dispersants, polyurethane-based polymer dispersants, polyallylamine-based polymer dispersants, and carbodiimide-based dispersants. From the viewpoint of improving the long-term storage stability of black pigment dispersions, it is preferable that the polymer dispersant has an amino group.

[0091] Methods for producing the photosensitive composition of the present invention include, for example, a method of directly dispersing component (a) in components (b), (c), (d) and an organic solvent using a disperser, or a method of preparing a black dispersion by dispersing component (a) in components (b) and an organic solvent using a disperser, and then mixing the black dispersion with components (c) and (d).

[0092] Examples of dispersers include bead mills, ball mills, sand grinders, three-roll mills, and high-speed impact mills. Among these, bead mills are preferred from the viewpoint of improving dispersion efficiency and achieving fine dispersion. Examples of bead mills include ball mills, basket mills, pin mills, and dyno mills. Examples of beads for bead mills include titania beads, zirconia beads, and zircon beads. The bead diameter for bead mills is preferably 0.03 to 1.0 mm. When the average primary particle diameter of component (a) and the particle diameter of secondary particles formed by the aggregation of primary particles are small, minute dispersion beads of 0.03 to 0.10 mm are preferred. In this case, a bead mill having a separator that uses a centrifugal separation method capable of separating the minute beads from the dispersion is preferred.

[0093] On the other hand, when dispersing component (a), which contains coarse particles of the submicron size, beads with a diameter of 0.10 mm or larger are preferred because sufficient grinding power can be obtained. The bead diameter can be calculated by measuring the equivalent circular diameter of 100 beads randomly selected by microscopic observation and calculating the number average value.

[0094] In the photosensitive composition of the present invention, it is preferable that the 50% cumulative diameter in the volume-based particle size distribution of the particle components in the photosensitive composition, as measured by dynamic light scattering, is 20 to 60 nm. Hereinafter, the above-mentioned 50% cumulative diameter may be referred to as the median diameter D50. When the median diameter D50 is 60 nm or less, the viscosity stability of the pigment dispersion is easily improved, high pattern linearity of the final cured product is easily obtained, and the occurrence of pixel non-illumination due to wiring short circuits in organic EL display devices having the cured product is easily avoided. Furthermore, when the median diameter D50 is 20 nm or more, more preferably 40 nm or more, the light shielding performance per unit weight is easily improved. The median diameter D50 is calculated as the cumulative volume average diameter with the finer particle size side as the base point (0%) using a dynamic light scattering particle size analyzer "nanoPartica SZ-100 (manufactured by Horiba, Ltd.)".

[0095] The photosensitive composition of the present invention may further contain the following component (e). (e) Ingredients: Silica particles.

[0096] Here, silica particles refer to particles in which the SiO2 content is 90% or more by weight excluding water, particles made of silicon dioxide (anhydrous silicic acid), particles made of silicon dioxide hydrate (hydrated silicic acid, white carbon), or particles made of quartz glass. Particles made of orthosilicic acid, metasilicic acid, and / or metadicilic acid are also included. The structure of the particles is not particularly limited and may have internal voids. Examples of controlled aggregation forms in the manufacturing process include bead-like silica, chain-like silica, associated silica, and marimo-like silica. These silica particles are considered to be secondary or tertiary particles composed of multiple primary particles.

[0097] In the photosensitive composition of the present invention, it is more preferable that the average primary particle diameter of component (e) is 10 to 30 nm. By setting the average primary particle diameter to 10 nm or more and 30 nm or less, the interaction between silica particles is maximized, reflow during curing is suppressed, and pattern linearity and mask bias can be improved.

[0098] (e) The average primary particle diameter of the component is the BET diameter and is calculated by the following method. BET diameter = 6 / ρS ρ: silica density (2.65 g / cm 3 ) S: BET specific surface area The silica sol or the dispersion liquid containing silica particles is heated and dried at 200 °C for 1 hour, and the obtained dried sample is vacuum degassed at 100 °C using the high-precision fully automatic gas adsorption device “BELSORP (registered trademark)” 36 manufactured by Bell Japan Co., Ltd., and then the adsorption isotherm at the liquid nitrogen temperature (77 K) of N2 gas is measured. This isotherm can be analyzed by the BET method to obtain the specific surface area S.

[0099] The photosensitive composition of the present invention contains the component (b-1), and the weight ratio W e / W b-1 of the component (e) and the component (b-1) is preferably 0.5 to 2.0. By setting the weight ratio W e / W b-1 to 0.5 or more, the reflow property during curing can be suppressed, and it is easy to improve the pattern linearity and mask bias. On the other hand, by setting the weight ratio W e / W b-1 to 2.0 or less, the occurrence of pattern peeling can be easily suppressed.

[0100] The photosensitive composition of the present invention contains the component (b-2), and the weight ratio W e / W b-2 of the component (e) and the component (b-2) is preferably 0.15 to 1.0. By setting the weight ratio W e / W b-2 to 0.15 or more, the reflow property during curing can be suppressed, and it is easy to improve the pattern linearity and mask bias. On the other hand, by setting the weight ratio W e / W b-2 to 1.0 or less, it shows an appropriate reflow property during curing, and it is easy to suppress the deterioration of the pattern linearity.

[0101] The cured product of the present invention is obtained by curing the photosensitive composition of the present invention.

[0102] A method for producing a cured product may include, for example, a step of applying a photosensitive composition, a step of drying the coating film, a step of exposing the coating film to light, a step of developing the exposed coating film, and a step of heat curing.

[0103] The details of each step are described below. In this invention, among the films formed on the substrate, the film formed after applying the photosensitive composition to the substrate and before heat curing is referred to as the coating film, and the film formed after heat curing is referred to as the cured product.

[0104] First, the process of applying the photosensitive composition will be described. In this process, the photosensitive composition of the present invention is applied to a substrate by methods such as spin coating, slit coating, dip coating, spray coating, or printing to obtain a coating film. Among these, the slit coating method is preferably used. The application speed in the slit coating method is generally in the range of 10 mm / second to 400 mm / second. The thickness of the coating film varies depending on the solid content concentration and viscosity of the photosensitive composition, but it is usually applied so that the film thickness after drying is 0.1 to 10 μm, preferably 1.0 to 5.0 μm.

[0105] Examples of substrates include glass, quartz, silicon, ceramic, plastic, and those on which electrodes such as ITO, Cu, and Ag are partially formed.

[0106] Prior to coating, the substrate to be coated with the photosensitive composition may be pre-treated with the adhesion improver described above. For example, one method is to treat the substrate surface using a solution in which the adhesion improver 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 at a concentration of 0.5 to 20% by weight. Examples of substrate surface treatment methods include spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.

[0107] Next, the drying process for the coating film will be described. In this process, the coating film is dried after the photosensitive composition has been applied. Drying in this process refers to either vacuum drying or heat drying. Both vacuum drying and heat drying may be performed, or only one of them may be performed.

[0108] This section describes the heating and drying process. This process is also called pre-baking. Drying is usually done using a hot plate, oven, or infrared heater. The heating temperature varies depending on the type and purpose of the coating, but it is preferable to heat it in the range of 50°C to 180°C for 1 minute to several hours.

[0109] Next, the process of exposing the coating film will be described. In this process, in order to form a pattern from the obtained coating film, it is preferable to irradiate the coating film with a chemical beam through a mask having a desired pattern and photo-cure the exposed area. Chemical beams that can be used for exposure include ultraviolet light, visible light, electron beams, and X-rays, but in the present invention, it is preferable to use the i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.

[0110] Next, the process of developing the exposed coating film will be described. In this process, after exposure, the unexposed areas are removed using a developer to form the desired pattern. Preferred developers are aqueous solutions of alkaline compounds such as tetramethylammonium hydroxide (hereinafter, TMAH), diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine. In some cases, polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and dimethylacrylamide, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added to these alkaline aqueous solutions, either individually or in combination of several.

[0111] In the case of photosensitive compositions containing a common black pigment, photocuring at the bottom is difficult, and when developed using a high-concentration alkaline developer such as 2.38 wt% TMAH, for example, it is difficult to process fine patterns. While it is possible to retain the pattern by reducing the double bond equivalent in the composition, this can lead to deterioration of the linearity of the pattern edges, or the over-cured layer on the film surface may peel off during development, causing residue at the pattern edges. The photosensitive composition of the present invention maintains a constant sensitivity while suppressing over-curing by light by setting the double bond equivalent of the solid content in the photosensitive composition in the range of 1000 g / mol to 3500 g / mol, thereby improving pattern linearity and reducing residue at the edges.

[0112] Next, it is preferable to rinse the pattern formed by development with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, or esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to the distilled water for rinsing.

[0113] Next, we will describe the heat curing process. In this process, if photocuring alone is insufficient, heat curing can further advance the reaction of radical polymerizable groups, thereby improving heat resistance. The heating temperature is preferably 150 to 300°C. The heating time is preferably 0.25 to 5 hours. The heating temperature may be changed continuously or in stages.

[0114] The organic EL display device of the present invention comprises the cured product of the present invention. The organic EL display device has at least a substrate, a first electrode, a second electrode, light-emitting pixels, a planarization layer, and a pixel splitting layer. An active matrix type organic EL display device having a plurality of pixels formed in a matrix is ​​preferred. The active matrix type organic EL display device has light-emitting pixels on a substrate such as glass, and a planarization layer provided to cover the lower part of the light-emitting pixels and the parts other than the light-emitting pixels. Furthermore, the planarization layer has a first electrode provided to cover at least the lower part of the light-emitting pixels and a second electrode provided to cover at least the upper part of the light-emitting pixels. In addition, the active matrix type organic EL display device has an insulating pixel splitting layer to split the light-emitting pixels, and the cured product of the present invention can be suitably used as the pixel splitting layer.

[0115] Furthermore, because the photosensitive composition of the present invention can form a highly detailed pattern that does not leave residue at the aperture, it can also be used as a black partition for solid-state image sensors, micro-LEDs, and mini-LED display devices, as well as a black matrix and black column spacer used in color filters for liquid crystal display devices. [Examples]

[0116] The present invention will be described in detail below with reference to examples and comparative examples, but the embodiments of the present invention are not limited thereto. Examples 13 and 19-38 are currently for reference only, while Examples 1-12, 14-18, and 39-46 are embodiments of the present invention. The names of the compounds used, for those that use abbreviations, are listed below.

[0117] Methyl methacrylate (MMA) Methacrylic acid (MAA) Styrene (St) 2-dimethylaminoethyl methacrylate (MLDA) 2-dimethylaminoethyl methacrylate hydrochloride (MLDA-Cl) 2-ethylhexyl methacrylate (2EHMA) 2-hydroxyethyl methacrylate (HEMA) Glycidyl methacrylate (GMA) Azobisisobutyronitrile (AIBN) Normal de decyl mercaptan (MDM) 4-Hydroxyphenyl methacrylate (PQMA).

[0118] <Evaluation Method> [Double bond equivalent] Using a potentiometric automatic titrator (AT-510; manufactured by Kyoto Electronics Manufacturing Co., Ltd.), the iodine value of the resin was measured by the Wies method, based on the method described in "Section 6 Iodine Value" of JIS K0070:1992 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical products". The iodine value of the resin was measured by the Wies method using an iodine monochloride solution (a mixed solution of iodine trichloride = 7.9 g, iodine = 8.9 g, and acetic acid = 1,000 mL) as the iodine source, a 100 g / L potassium iodide aqueous solution as the capture aqueous solution for unreacted iodine, and a 0.1 mol / L sodium thiosulfate aqueous solution as the titration reagent. The iodine value of the resin was measured by the Wies method, based on the method described in "Section 6 Iodine Value" of JIS K0070:1992 "Test methods for acid value, saponification value, ester value, iodine value, hydroxyl value, and unsaponifiable matter of chemical products". The double bond equivalent (unit: g / mol) was calculated from the measured iodine value (unit: gI / 100 g).

[0119] [Calculation of median diameter D50] Measurement sample: The photosensitive compositions obtained in each example and comparative example were mixed with PGMEA in three equal portions such that the weight ratio of photosensitive composition / PGMEA was 1 / 99, and stirred on a shaker for 10 minutes. Measuring device: Dynamic light scattering particle size distribution measuring device "nanoPartica SZ-100 (manufactured by Horiba, Ltd.)" Light source: Wavelength 532 nm / 10 mW (semiconductor-excited solid-state laser) Liquid temperature of the measurement sample: 25 ± 1 °C (under atmospheric pressure) Calculation method: The cumulative 50% diameter based on the light scattering intensity was determined, the average value of three measurements was calculated, and the value obtained by rounding off the first decimal place was taken as the median diameter D50.

[0120] [Sensitivity] The photosensitive compositions obtained in each example and comparative example were applied onto an ITO substrate using a spinner (MS-A150 manufactured by Mikasa Co., Ltd.) to achieve a predetermined film thickness, and heated and dried on a hot plate at 100 °C for 2 minutes. For this coating film, using a mask aligner (PEM-6M manufactured by Union Optical Co., Ltd.) and through a negative mask 1 (negative mask having a pattern with a minimum line and space of 1 μm, a maximum of 50 μm, and a pitch of 1 μm) manufactured by HOYA Co., Ltd., with a high-pressure mercury lamp as the light source, an exposure was performed with a maximum exposure amount of 500 mJ / cm 2 and the exposure amount was decreased by 10 mJ / cm 2 each time for exposure, and a patterned substrate was obtained by developing for 60 seconds with an alkaline developer of 2.38 wt% TMAH aqueous solution. Next, the obtained patterned substrate was baked in a hot air oven at 230 °C for 60 minutes to obtain a cured product. At the film thickness (T PB ) μm after pre-baking and the film thickness (T DEV ) μm after development, the minimum exposure amount at which the remaining film rate after development ((T DEV ) / (T PB ) × 100) was 70% or more was defined as the sensitivity.

[0121] Evaluation A: Less than 50 mJ / cm 2 B: 50 mJ / cm or more and less than 100 mJ / cm 2 2 ​​​ C: 100mJ / cm 2 More than 200mJ / cm 2 less than D: 200 mJ / cm 2 That's all.

[0122] [Minimum Pattern] The patterned substrates obtained from each example and comparative example were observed with an optical microscope, and the smallest line-and-space pattern without any chipping or peeling in the pattern area was defined as the minimum pattern.

[0123] evaluation A: Minimum pattern 1-4 μm B: Minimum pattern 5-9 μm C: Minimum pattern 10-14 μm D: Minimum pattern 15-19 μm E: Minimum pattern size 20 μm or larger.

[0124] [Pattern Linearity] The patterned substrates obtained in each example and comparative example were observed with an optical microscope, and the aperture dimensions in a line-and-space pattern with a mask aperture width of 50 μm were measured at 10 points every 10 μm. The difference W (μm) between the maximum and minimum widths was calculated using the following method. The smaller the difference between the maximum and minimum widths, the higher the pattern linearity and the better the visibility of the organic EL display device.

[0125] evaluation S: The difference W between the maximum and minimum width is less than 0.3 μm. A: The difference W between the maximum width and minimum width is 0.3 μm or more and less than 0.5 μm. B: The difference W between the maximum and minimum widths is 0.5 μm or more and less than 1.0 μm. C: The difference W between the maximum and minimum widths is 1.0 μm or more and less than 2.0 μm. D: The difference W between the maximum and minimum width is 2.0 μm or more. [Residue] The patterned substrates obtained from each example and comparative example were observed with an optical microscope, and the number of development residue particles with a major axis of 0.1 μm or more and less than 3.0 μm at each aperture was counted. The average number of development residue particles observed per 50 μm aperture was evaluated based on the following criteria.

[0126] evaluation A: No development residue is visible at all. B: Fewer than 5 residue particles are observed. C: Five or more but fewer than ten development residues are observed. D: More than 10 but less than 20 development residues are observed. E: More than 20 development residues are visible.

[0127] [Mask bias] For each example and comparative example, the aperture width of a 50 μm line-and-space pattern at the minimum exposure required to form a pattern was measured using an optical microscope. The smaller the absolute difference between the mask design value and the aperture width of the cured product, the smaller the mask bias and the better the result was judged to be.

[0128] evaluation S: Mask bias less than 0.6 μm A: Mask bias 0.6 μm or more and less than 1.0 μm B: Mask bias 1.0 μm or more and less than 2.0 μm C: Mask bias 2.0 μm or more and less than 3.0 μm D: Mask bias of 3.0 μm or more.

[0129] [Display characteristics of OLED display devices] Figure 1 shows a schematic diagram of the procedure for fabricating organic EL display devices using the photosensitive compositions obtained in each example and comparative example. First, a 10 nm transparent conductive ITO film was formed on the entire surface of a 38 mm × 46 mm alkali-free glass substrate 1 by sputtering and etched as the first electrode (transparent electrode) 2. At the same time, an auxiliary electrode 3 for extracting the second electrode was also formed. The obtained substrate was ultrasonically cleaned for 10 minutes with Semicoclean 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) and then washed with ultrapure water. Next, the photosensitive compositions obtained in each example and comparative example were applied to the entire surface of this substrate by spin coating and pre-baked on a hot plate at 100°C for 2 minutes. After exposing this film to the minimum exposure of each photosensitive composition using a high-pressure mercury lamp as the light source via a photomask, it was developed with a 2.38 wt% TMAH aqueous solution to dissolve unwanted parts and rinsed with pure water. The obtained resin pattern was heat-treated in a hot air oven at 230°C for 60 minutes. In this way, an insulating layer 4 was formed, limited to the effective area of ​​the substrate, with openings measuring 70 μm in width and 260 μm in length, arranged at a pitch of 155 μm in the width direction and 465 μm in the length direction, with each opening exposing the first electrode. In this manner, an insulating layer with an insulating layer opening ratio of 25% was formed in the effective area of ​​the substrate, which was a rectangle with sides of 16 mm. The thickness of the insulating layer was approximately 1.5 μm.

[0130] Next, after nitrogen plasma treatment as a pretreatment, an organic EL layer 5 including the light-emitting layer was formed by vacuum deposition. The vacuum level during deposition was 1 × 10⁻⁶. -3 The temperature was below Pa, and the substrate was rotated relative to the deposition source during deposition. First, compound (HT-1) was deposited as a hole injection layer at 10 nm, and compound (HT-2) was deposited as a hole transport layer at 50 nm. Next, compound (GH-1) as a host material and compound (GD-1) as a dopant material were deposited on the light-emitting layer to a thickness of 40 nm with a doping concentration of 10%. Then, compound (ET-1) and compound (LiQ) were layered as electron transport materials in a volume ratio of 1:1 to a thickness of 40 nm. The structures of the compounds used in the organic EL layer are shown below.

[0131] [ka]

[0132] Next, after depositing a 2nm layer of compound (LiQ), Mg and Ag were deposited in a volume ratio of 10:1 to form a 10nm layer of Mg and Ag to create the second electrode (non-transparent electrode) 6. Finally, the cap-shaped glass plate was sealed by bonding it with an epoxy resin adhesive under a low-humidity nitrogen atmosphere, and four top-emission type organic EL display devices, each with sides of 5mm, were fabricated on a single substrate. The film thickness referred to here is the value displayed on a quartz crystal-wavelength film thickness monitor.

[0133] For each embodiment, a total of 20 organic EL display devices were created using the method described above, and display tests were conducted.

[0134] evaluation A: All pixels light up B: 1 to 4 non-lighting devices C: There are 5 or more non-illuminated devices.

[0135] <Manufacturing example> (Synthesis Example 1: Alkali-soluble resin P-1) 160.0g of PGMEA was placed in a pressure vessel equipped with a stirrer, thermometer, reflux condenser, and dropper pump. The reaction vessel was filled with nitrogen and heated to 90°C. A mixture of 8.97g of St, 9.97g of MMA, 0.55g of MLDA, 6.06g of MAA, 12.75g of 2EHMA, and two polymerization initiators, AIBN 2.0g and MDM 3.0g, was added dropwise using a dropper pump over 3 hours to carry out copolymerization. Subsequently, the reaction vessel was purged with air, and 2.24g of GMA was added dropwise using a dropper pump over 1 hour to carry out the addition reaction. The contents of the vessel were then stirred for a further 2 hours. As a result, an alkali-soluble resin (P-1) solution with a solid content of 20% by weight was obtained, having characteristic values ​​of amine value 5mgKOH / g, acid value 76mgKOH / g, double bond equivalent 2540g / mol, and weight-average molecular weight 7000.

[0136] (Synthesis Example 2: Alkali-soluble resin P-2) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 9.03 g of St, 10.01 g of MMA, 0.09 g of MLDA, 6.08 g of MAA, and 12.79 g of 2EHMA, and the amount of GMA added was 2.24 g, resulting in an alkali-soluble resin (P-2) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 1 mg KOH / g, acid value 76 mg KOH / g, double bond equivalent 2532 g / mol, and weight-average molecular weight 7000.

[0137] (Synthesis Example 3: Alkali-soluble resin P-3) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 8.92 g of St, 10.00 g of MMA, 0.23 g of MLDA, 6.07 g of MAA, and 12.77 g of 2EHMA, and the amount of GMA added was 2.24 g, resulting in an alkali-soluble resin (P-3) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 2 mg KOH / g, acid value 77 mg KOH / g, double bond equivalent 2534 g / mol, and weight-average molecular weight 7200.

[0138] (Synthesis Example 4: Alkali-soluble resin P-4) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 8.31 g of St, 9.94 g of MMA, 1.01 g of MLDA, 6.04 g of MAA, and 12.71 g of 2EHMA, and the amount of GMA added was 2.23 g, resulting in an alkali-soluble resin (P-4) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 10 mg KOH / g, acid value 76 mg KOH / g, double bond equivalent 2548 g / mol, and weight-average molecular weight 7000.

[0139] (Synthesis Example 5: Alkali-soluble resin P-5) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 7.49 g of St, 9.87 g of MMA, 2.05 g of MLDA, 6.00 g of MAA, and 12.62 g of 2EHMA, and the amount of GMA added was 2.21 g, resulting in an alkali-soluble resin (P-5) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 20 mg KOH / g, acid value 76 mg KOH / g, double bond equivalent 2566 g / mol, and weight-average molecular weight 7300.

[0140] (Synthesis Example 6: Alkali-soluble resin P-6) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 7.10 g of St, 9.84 g of MMA, 2.54 g of MLDA, 5.98 g of MAA, and 12.57 g of 2EHMA, and the amount of GMA added was 2.21 g, resulting in an alkali-soluble resin (P-6) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 25 mg KOH / g, acid value 76 mg KOH / g, double bond equivalent 2575 g / mol, and weight-average molecular weight 7100.

[0141] (Synthesis Example 7: Alkali-soluble resin P-7) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 6.99 g of St, 9.64 g of MMA, 3.28 g of MLDA-Cl, 5.85 g of MAA, and 12.31 g of 2EHMA, and the amount of GMA added was 2.16 g, resulting in an alkali-soluble resin (P-7) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 24 mg KOH / g, acid value 75 mg KOH / g, double bond equivalent 2629 g / mol, and weight-average molecular weight 7200.

[0142] (Synthesis Example 8: Alkali-soluble resin P-8) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 7.10 g of St, 9.74 g of MMA, 1.21 g of MLDA, 1.63 g of MLDA-Cl, 5.92 g of MAA, and 12.45 g of 2EHMA, and the amount of GMA added was 2.16 g, resulting in an alkali-soluble resin (P-8) solution with a solid content of 20% by weight, exhibiting characteristic values ​​of amine value 24 mg KOH / g, acid value 75 mg KOH / g, double bond equivalent 2600 g / mol, and weight-average molecular weight 7500.

[0143] (Synthesis Example 9: Alkali-soluble resin P-9) Using the same method as in Synthesis Example 1, the copolymer monomers to be added were 9.15 g of St, 10.02 g of MMA, 6.06 g of MAA, and 12.81 g of 2EHMA, and the amount of GMA added was 2.20 g. This yielded an alkali-soluble resin (P-9) solution with a solid content of 20% by weight, which had no amine value and possessed the characteristic values ​​of an acid value of 77 mg KOH / g, a double bond equivalent of 2581 g / mol, and a weight-average molecular weight of 6900.

[0144] (Synthesis Example 10: Phenolic hydroxyl group-containing resin H-1) A phenolic hydroxyl group-containing resin H-1 with a hydroxyl value of 384 mgKOH / g was synthesized by the method described in Example 1 of Japanese Patent Publication No. 2015-74717. 20 g of H-1 was added to 80 g of PGMEA to dissolve the resin, thereby obtaining a 20% by weight solids solution of H-1. The weight-average molecular weight of the resulting reactant was 8800.

[0145] (Synthesis Example 11: Phenolic hydroxyl group-containing resin H-2) 25.34 g of PQMA, 4.28 g of MMA, and 10.38 g of St were completely dissolved in 100.0 g of PGMEA, and 3.66 g of V-601 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator was completely dissolved in 15.0 g of PGMEA. The two resulting solutions were simultaneously added dropwise over 2 hours to 45.0 g of PGMEA heated to 85°C in a 300 mL three-necked flask under a nitrogen gas atmosphere. After the addition was complete, the mixture was reacted at 85°C for 3 hours to obtain a 20 wt% solids solution of hydroxyl group-containing resin H-2 with a hydroxyl value of 101 mg KOH / g. The weight-average molecular weight of the resulting reactant was 8800.

[0146] (Synthesis Example 12: Hydroxyl group-containing resin H-3) Using the same method as in Synthesis Example 11, the copolymer monomers added were HEMA 8.70 g, MAA 8.93 g, MMA 6.70 g, and St 15.67 g to obtain a 20 wt% solids solution of hydroxyl group-containing resin H-3 with a hydroxyl value of 94 mg KOH / g and an acid value of 70 mg KOH / g. The weight-average molecular weight of the resulting reactant was 8500.

[0147] (Synthesis Example 13: Hydroxyl group-containing resin H-4) Using the same method as in Synthesis Example 11, the copolymer monomers added were HEMA 6.18 g, MAA 9.07 g, MMA 8.84 g, and St 15.91 g to obtain a 20 wt% solids solution of hydroxyl group-containing resin H-4 with a hydroxyl value of 66 mg KOH / g and an acid value of 71 mg KOH / g. The weight-average molecular weight of the obtained reactant was 8600.

[0148] (Synthesis Example 14: Hydroxyl group-containing resin H-5) Using the same method as in Synthesis Example 11, a 20% by weight solids solution of hydroxyl group-containing resin H-5 was obtained by adding 4.90 g of HEMA, 9.13 g of MAA, 9.93 g of MMA, and 16.03 g of St as copolymer monomers, with a hydroxyl value of 53 mg KOH / g and an acid value of 72 mg KOH / g. The weight-average molecular weight of the resulting reactant was 8700.

[0149] (Manufacturing Example 1: Manufacturing of Black Pigment Dispersion (DB-1)) 375 g of Irgaphor Black S0100CF (BASF) as the black pigment (a-1), 937.5 g of a 20 wt% PGMEA solution of alkali-soluble resin (P-1), 187.5 g of a polymer dispersant with an amine value of 20 mg KOH / g as described in Synthesis Example 2 of Japanese Patent Publication No. 2020-070352, and 1500 g of PGMEA were placed in a tank and stirred for 20 minutes with a homomixer to obtain a preliminary dispersion. The obtained preliminary dispersion was supplied to an Ultra Apex Mill disperser manufactured by Hiroshima Metal & Machinery Co., Ltd., which is equipped with a centrifugal separator packed with 0.10 mmφ zirconia beads at 70 volume%, and dispersion was carried out at a rotation speed of 10 m / s for 3 hours to obtain a black pigment dispersion (DB-1) with a solid content concentration of 25 wt% and a black pigment / resin (weight) ratio of 80 / 20.

[0150] (Manufacturing Examples 2-5: Manufacturing of Black Pigment Dispersions (DB-2)-(DB-5)) Using the same method as in Manufacturing Example 1, (DB-2) was obtained by setting the dispersion time to 6 hours, (DB-3) by setting the dispersion time to 4 hours, (DB-4) by setting the dispersion time to 2 hours, and (DB-5) by setting the dispersion time to 1 hour.

[0151] (Manufacturing Examples 6-7: Manufacturing of Black Pigment Dispersion (DB-6)-(DB-7)) Using the same method as in Manufacturing Example 1, (DB-6) was obtained by using (a-2) titanium nitride (manufactured by Nisshin Engineering) as the added black pigment, and (DB-7) was obtained by using (a-3) carbon black (TPK1227 manufactured by Cabot) with a surface modified by sulfonic acid groups as the added pigment.

[0152] (Manufacturing Example 8: Manufacturing of Black Pigment Dispersion (DB-8)) (DB-8) was obtained by using the same method as in Production Example 1, with 468.8 g of alkali-soluble resin (P-1) and 468.8 g of phenolic hydroxyl group-containing resin H-1 added.

[0153] (Manufacturing Examples 9-16: Manufacturing of Black Pigment Dispersions (DB-9)-(DB-16)) Using the same method as in Production Example 1, (DB-9) to (DB-16) were obtained by using alkali-soluble resins (P-2) to (P-9) respectively.

[0154] (Example 1) To 120.00 g of a black pigment dispersion (DB-1), 37.50 g of a 20 wt% PGMEA solution of alkali-soluble resin (P-1), 112.50 g of hydroxyl group-containing resin (H-1), 3.68 g of Irgacure OXE-03 (manufactured by BASF Ltd.) as a photopolymerization initiator, 11.25 g of HX-220 (manufactured by Nippon Kayaku Co., Ltd.) as a radical polymerizable compound, 0.08 g of silicone-based surfactant "BYK" (registered trademark) 333 (manufactured by BY Chemie Inc.), and 215.00 g of PGMEA were added to obtain a photosensitive composition (PB-1) with a solid content concentration of 15 wt% and a black pigment / resin (weight ratio) of 20 / 80. Furthermore, a cured product of the obtained photosensitive composition and an organic EL display device equipped with the cured product were prepared according to the method described above.

[0155] (Example 2) In the same manner as in Example 1, a photosensitive composition (PB-2), its cured product, and an organic EL display device comprising the cured product were obtained by adding 5.63 g of HX-220 and 5.63 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) (hereinafter sometimes referred to as DPHA) as radical polymerizable compounds.

[0156] (Example 3) In the same manner as in Example 1, a photosensitive composition (PB-3), its cured product, and an organic EL display device comprising the cured product were obtained by adding 37.50 g of alkali-soluble resin (P-1), 131.25 g of hydroxyl group-containing resin (H-1), and 37.50 g of radical polymerizable compound HX-220.

[0157] (Example 4) In the same manner as in Example 1, a photosensitive composition (PB-4), its cured product, and an organic EL display device comprising the cured product were obtained by using BPE-900 (manufactured by Shin-Nakamura Chemical Co., Ltd.) as the type of radical polymerizable compound to be introduced.

[0158] (Example 5) In the same manner as in Example 1, the alkali-soluble resin (P-1) was omitted, the amount of hydroxyl group-containing resin (H-1) to be added was set to 150.00 g, and the type of radical polymerizable compound to be added was set to BPE-900 to obtain a photosensitive composition (PB-5), its cured product, and an organic EL display device comprising the cured product.

[0159] (Examples 6-11) In the same manner as in Example 1, the black pigment dispersions to be added were designated as (DB-2) to (DB-7), respectively, to obtain photosensitive compositions (PB-6) to (PB-11), their cured products, and an organic EL display device comprising the cured products.

[0160] (Example 12) Using the same method as in Example 1, by using Adeka Arcles® NCI-831 as the photopolymerization initiator, (PB-12), its cured product, and an organic EL display device equipped with the cured product were obtained.

[0161] (Example 13) In the same manner as in Example 1, (PB-13), its cured product, and an organic EL display device comprising the cured product were obtained by using a black pigment dispersion containing 120.0 g of (DB-8), 168.75 g of hydroxyl group-containing resin (H-1), 37.50 g of HX-220, 3.68 g of NCI-831, and 0.08 g of BYK333.

[0162] (Example 14) Using the same method as in Example 13, (PB-14), its cured product, and an organic EL display device comprising the cured product were obtained by using (DB-1) as the black pigment dispersion.

[0163] (Example 15) In the same manner as in Example 1, (PB-15), its cured product, and an organic EL display device comprising the cured product were obtained by using the same method as in Example 1, with a black pigment dispersion containing 120.0 g of (DB-1), 18.75 g of alkali-soluble resin (P-1), 150.00 g of hydroxyl group-containing resin (H-1), 37.50 g of HX-220, 3.68 g of NCI-831, and 0.08 g of BYK333.

[0164] (Example 16) Using the same method as in Example 1, (PB-16), its cured product, and an organic EL display device comprising the cured product were obtained by using a black pigment dispersion with 120.0 g of (DB-1), 56.25 g of alkali-soluble resin (P-1), 112.50 g of hydroxyl group-containing resin (H-1), 37.50 g of HX-220, 3.68 g of NCI-831, and 0.08 g of BYK333.

[0165] (Example 17) Using the same method as in Example 1, (PB-17), its cured product, and an organic EL display device comprising the cured product were obtained by using a black pigment dispersion with 120.0 g of (DB-1), 75.00 g of alkali-soluble resin (P-1), 93.75 g of hydroxyl group-containing resin (H-1), 37.50 g of HX-220, 3.68 g of NCI-831, and 0.08 g of BYK333.

[0166] (Example 18) In the same manner as in Example 1, (PB-18), its cured product, and an organic EL display device comprising the cured product were obtained by using a black pigment dispersion with 120.0 g of (DB-1), 86.25 g of alkali-soluble resin (P-1), 82.50 g of hydroxyl group-containing resin (H-1), 37.50 g of HX-220, 3.68 g of NCI-831, and 0.08 g of BYK333.

[0167] (Example 19) In the same manner as in Example 1, (PB-19), its cured product, and an organic EL display device comprising the cured product were obtained by using the same method as in Example 1, with a black pigment dispersion containing 120.0 g of (DB-1), 93.75 g of (P-1), 75.00 g of (H-1), 37.50 g of HX-220, 3.68 g of NCI-831, and 0.08 g of BYK333.

[0168] (Examples 20-23) Using the same method as in Example 19, the hydroxyl group-containing resins to be added were (H-2) to (H-5), (PB-20) to (PB-23), and the cured products thereof and an organic EL display device comprising the cured products were obtained.

[0169] (Examples 24-31) In the same manner as in Example 19, the pigment dispersions to be added were (DB-9) to (DB-16), the alkali-soluble resins were (P-2) to (P-9), and the hydroxyl group-containing resin was (H-5), thereby obtaining (PB-24) to (PB-31), their cured products, and an organic EL display device comprising the cured products.

[0170] (Example 32) In the same manner as in Example 31, the radical polymerizable compounds to be added were 30.00 g of HX-220 and 7.50 g of DPHA to obtain (PB-32), its cured product, and an organic EL display device equipped with the cured product.

[0171] (Example 33) In the same manner as in Example 31, the radical polymerizable compounds added were 22.50 g of HX-220 and 15.00 g of DPHA to obtain (PB-33), its cured product, and an organic EL display device equipped with the cured product.

[0172] (Example 34) In the same manner as in Example 31, the radical polymerizable compounds to be added were 18.75 g of HX-220 and 18.75 g of DPHA to obtain (PB-34), its cured product, and an organic EL display device equipped with the cured product.

[0173] (Example 35) In the same manner as in Example 31, 37.50 g of A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used as the radical polymerizable compound to be added, thereby obtaining (PB-35), its cured product, and an organic EL display device equipped with the cured product.

[0174] (Example 36) In the same manner as in Example 31, the radical polymerizable compounds to be added were 18.75 g of A-BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 18.75 g of DPHA to obtain (PB-36), its cured product, and an organic EL display device equipped with the cured product.

[0175] (Example 37) In the same manner as in Example 31, PB-37, its cured product, and an organic EL display device comprising the cured product were obtained by adding 18.75 g of BPE-900 and 18.75 g of DPHA as radical polymerizable compounds.

[0176] (Example 38) In the same manner as in Example 31, 18.75 g of BPE-1300N (manufactured by Shin-Nakamura Chemical Co., Ltd.) and 18.75 g of DPHA were added as radical polymerizable compounds to obtain (PB-38), its cured product, and an organic EL display device equipped with the cured product.

[0177] (Example 39) In the same manner as in Example 1, 18.75 g of a 20 wt% PGMEA solution of (P-1), 93.75 g of hydroxyl group-containing resin (H-1), 3.68 g of Irgacure OXE-03, 11.25 g of HX-220, 0.08 g of "BYK" (registered trademark) 333, 37.5 g of "Snowtex" (registered trademark) ST-XS (manufactured by Nissan Chemical Corporation) as silica particles, and 214.99 g of PGMEA were added to 120.00 g of (DB-1) to obtain a photosensitive composition (PB-39), its cured product, and an organic EL display device comprising the cured product.

[0178] (Example 40) In the same manner as in Example 39, 25.00 g of “Organosilica Sol” (registered trademark) MIBK-ST (manufactured by Nissan Chemical Corporation) and 227.49 g of PGMEA were added as silica particles to obtain a photosensitive composition (PB-40), its cured product, and an organic EL display device comprising the cured product.

[0179] (Example 41) In the same manner as in Example 40, by changing the type of silica particles added to "Organosilica Sol" (registered trademark) CHO-ST-M (manufactured by Nissan Chemical Corporation), a photosensitive composition (PB-41), its cured product, and an organic EL display device comprising the cured product were obtained.

[0180] (Example 42) In the same manner as in Example 40, by changing the type of silica particles added to "Organosilica Sol" (registered trademark) MIBK-ST-L (manufactured by Nissan Chemical Corporation), a photosensitive composition (PB-42), its cured product, and an organic EL display device comprising the cured product were obtained.

[0181] (Example 43) In the same manner as in Example 40, (PB-43), its cured product, and an organic EL display device comprising the cured product were obtained by adding 33.75 g of (P-1), 105.00 g of (H-1), 7.50 g of MIBK-ST, and 218.74 g of PGMEA.

[0182] (Example 44) In the same manner as in Example 40, by setting the amounts of (P-1) to be input as 30.00 g, (H-1) as 101.25 g, MIBK-ST as 12.50 g, and PGMEA as 221.24 g, (PB-44) and its cured product and an organic EL display device including the cured product were obtained.

[0183] (Example 45) In the same manner as in Example 40, by setting the amounts of (H-1) to be input as 75.00 g, HX-220 as 7.500 g, MIBK-ST as 50.00 g, and PGMEA as 224.99 g, (PB-45) and its cured product and an organic EL display device including the cured product were obtained.

[0184] (Example 46) In the same manner as in Example 40, by setting the amounts of (H-1) to be input as 56.25 g, HX-220 as 7.500 g, MIBK-ST as 62.50 g, and PGMEA as 231.24 g, (PB-46) and its cured product and an organic EL display device including the cured product were obtained.

[0185] (Comparative Example 1) In the same manner as in Example 31, by setting the amount of the radical polymerizable compound to be input as 37.50 g of DPHA, (PB-47) and its cured product and an organic EL display device including the cured product were obtained.

[0186] (Comparative Example 2) In the same manner as in Example 31, by setting the amount of the radical polymerizable compound to be input as 37.50 g of BPE-1300N, (PB-48) and its cured product and an organic EL display device including the cured product were obtained.

[0187] The composition of the black pigment dispersion is shown in Table 1. Also, the compositions of each example and comparative example are shown in Tables 2 and 4, and their evaluation results are shown in Tables 3 and 5.

[0188]

Table 1

[0189]

Table 2-1

[0190]

Table 2-2

[0191]

Table 2-3

[0192] <00OO932>

Table 2-4

[0193]

Table 3-1

[0194]

Table 3-2

[0195]

Table 4-1

[0196] [[ID=SS]] (这里原文的“ ”前面的“SS”疑似错误,按照规则保留原文)

Table 4-2

[0197] <OO00967>(这里原文的“ ”中的“OO”疑似错误,按照规则保留原文)

Table 5

[0198] The photosensitive composition described in the examples has high light-shielding properties and sensitivity, while having excellent pattern linearity, small residue at the edge part, and small mask bias. In addition, the frequency of occurrence of non-light-emitting pixels in the organic EL display device using the cured product is low.

[0199] On the other hand, the photosensitive compositions of the comparative examples differed. In Comparative Example 1, the photosensitive composition had a small amount of double bond equivalents in the solid content, resulting in excessive photocuring in the exposed areas. This led to poor linearity at the pattern edges, and the over-hardened layer on the film surface peeled off during development, leaving residue at the pattern edges. In Comparative Example 2, the photosensitive composition had a large amount of double bond equivalents in the solid content, resulting in insufficient crosslinking density in the exposed areas. This resulted in poor fine-line processing and a tendency for pattern peeling. [Explanation of symbols]

[0200] 1: Alkali-free glass substrate 2: First electrode (transparent electrode) 3: Auxiliary electrode 4: Insulating layer 5: Organic EL layer 6: Second electrode (non-transparent electrode)

Claims

1. A photosensitive composition comprising all of the following components (a) to (d), wherein the double bond equivalent of the solid content in the photosensitive composition is 1000 to 3500 g / mol, and the (b) component contains the following component (b-1), and the (b) component contains the following component (b-2), and the weight ratio W b-1 / W b-2 of the (b-1) component to the (b-2) component is 0.2 to 1.

5. (a) Ingredients: Black pigment (b) Component: Alkali-soluble resin (b-1) Component: Alkali-soluble resin with an amine value of 2.0 to 10.0 mg KOH / g. (b-2) Component: Resin that does not have the structural unit represented by formula (1) or the structural unit represented by formula (2), and has a hydroxyl value of 60 mg KOH / g or more. (c) Component: Radical polymerizable compound (d) Component: Photopolymerization initiator 【Chemistry 1】 【Chemistry 2】 (In formula (1), R1 is a hydrogen atom or a methyl group, R2 is any of the following selected from alkylene groups having 1 to 4 carbon atoms, divalent alkyleneoxyalkylene groups having 2 to 4 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and R3 and R4 each independently represent any of the following selected from alkyl groups having 1 to 4 carbon atoms, alkoxyalkyl groups having 2 to 4 carbon atoms, alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and aromatic hydrocarbon groups having 6 to 10 carbon atoms.) In formula (2), R5 is a hydrogen atom or a methyl group; R6 is any of the following selected from alkylene groups having 1 to 4 carbon atoms, divalent alkyleneoxyalkylene groups having 2 to 4 carbon atoms, divalent alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and divalent aromatic hydrocarbon groups having 6 to 10 carbon atoms; R7, R8, and R9 are each independently selected from alkyl groups having 1 to 4 carbon atoms, alkoxyalkyl groups having 2 to 4 carbon atoms, alicyclic hydrocarbon groups having 3 to 6 carbon atoms, and aromatic hydrocarbon groups having 6 to 10 carbon atoms; and X represents any of the following: a bromine atom, a chlorine atom, an iodine atom, a bisulfate, and a hydroxide.

2. The photosensitive composition according to claim 1, wherein the (c) component comprises the (c-1) component described below. (c-1) Component: A radical polymerizable compound having two ethylenically unsaturated bonds in its molecule and a double bond equivalent of 200 to 600 g / mol.

3. The photosensitive composition according to claim 2, wherein the content of component (c-1) is 60 to 100% by weight of component (c).

4. The photosensitive composition according to claim 1, wherein the (b-1) component comprises a structural unit represented by formula (1) and / or a structural unit represented by formula (2) and a structural unit represented by formula (3). 【Transformation 3】 (In formula (3), R １０ and R １１ Each is independently a hydrogen atom or a methyl group, R １２ (This represents one of the following: an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms.)

5. The photosensitive composition according to claim 1, wherein the (d) component contains an oxime ester-based photopolymerization initiator having a fluorine atom in the molecule.

6. The photosensitive composition according to claim 1, wherein the component (a) contains at least one compound selected from the group consisting of a compound represented by formula (4), a compound represented by formula (5), and isomers thereof. 【Chemistry 4】 (In Formulas (4) and (5), R １３ and R １８ each independently represents a hydrogen atom, CH ３ CF ３ or a fluorine atom. R １４ , R １５ , R １６ , R １７ , R １９ , R ２０ , R ２１ and R ２２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, COOH, COOR ２３ , COO － , CONH ２ , CONHR ２３ , CONR ２３ R ２４ , CN, OH, OR ２３ , OCOR ２３ , OCONH ２ , OCONHR ２３ , OCONR ２３ R ２４ . R ２３ and R ２４ each independently represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, a cycloalkenyl group having 1 to 12 carbon atoms or an alkynyl group having 1 to 12 carbon atoms.).

7. The photosensitive composition according to claim 1, wherein the 50% cumulative diameter in the volume-based particle size distribution of the particulate components in the photosensitive composition, as measured by dynamic light scattering, is 20 to 60 nm.

8. The photosensitive composition according to claim 1, further comprising the following component (e). (e) Ingredients: Silica particles

9. The photosensitive composition according to claim 8, wherein the average primary particle size of component (e) is 10 to 30 nm.

10. The above (b-1) component is contained, and the weight ratio W of the above (e) component to the above (b-1) component is ｅ / W ｂ－１ The photosensitive composition according to claim 8, wherein is 0.5 to 2.

0.

11. The weight ratio W of component (e) and component (b-2) ｅ / W ｂ－２ The photosensitive composition according to claim 8, wherein the ratio is 0.15 to 1.

0.

12. A cured product obtained by curing the photosensitive composition according to any one of claims 1 to 11.

13. An organic EL display device comprising the cured product described in claim 12.

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