Colorant dispersion, photosensitive resin composition, and cured product

Abstract

The present invention relates to a colorant dispersion liquid having storage stability, comprising: a colorant, a dispersant, a benzene sulfonic acid compound having a fluoroalkyl side chain, and an organic solvent. When a photosensitive resin composition containing the colorant dispersion liquid is used, black pigment particle precipitates produced upon long-term storage can be avoided, and high light-blocking properties are maintained even upon long-term storage.

Description

TECHNICAL FIELD

[0001] The present application relates to a colorant dispersion liquid and a negative photosensitive resin composition, a cured product manufactured using the same. BACKGROUND

[0002] In recent years, OLED display devices have rapidly spread in terminal products such as mobile phones, electronic watches, tablet computers, and personal computers due to their excellent response speed, higher brightness, and contrast, and other advantages. As a self-luminous display device, the OLED display device has the problem of reduced visibility due to the incidence of ambient light, and thus a polarizing plate is required to reduce the reflection of ambient light on the screen to improve the contrast and color performance of the OLED display device. However, due to the presence of the polarizing plate, the theoretical transmittance of the display light emitted by the OLED device is only 50%, and thus the luminous brightness of the OLED device needs to be improved to compensate for the loss of transmittance, resulting in the problem of insufficient energy efficiency of the OLED.

[0003] In recent years, the COE technology (Color filter On Encapsulation) has appeared, which reduces the external light reflection of ambient light by the light-shielding property imparted by the black pixel definition layer, avoiding the problem of reduced light extraction efficiency caused by the use of a polarizing plate, thereby greatly reducing the energy consumption of the OLED display device and further improving the contrast.

[0004] As a coloring material for the black pixel definition layer, a negative black resin composition using a black pigment is disclosed (for example, see Patent Documents 1, 2, 3, and 4). The negative coloring resin composition is mainly composed of: a pigment dispersion liquid, an alkali-soluble resin, a photopolymerization initiator, an olefinically unsaturated compound, and an organic solvent.

[0005] Patent Document 1: International Publication No. 2018 / 181311

[0006] Patent Document 2: International Publication No. 2022 / 172780

[0007] Patent Document 3: International Publication No. 2013 / 175978

[0008] Patent Document 4: International Publication No. 2022 / 176976

[0009] As a coloring material for blackening the pixel separation layer, it is preferable to use an organic pigment having both high insulating properties and low dielectric constant, compared to inorganic black pigments such as carbon black. However, the existing colorant dispersion liquid has insufficient stability, and there is a problem of colorant flocculation during long-term storage, and thus problems such as an increase in the particle size of the colorant, a decrease in the storage stability of the resin composition, and a decrease in the light-shielding property of the cured film occur during use, further causing problems such as clogging of the coating knife head and a decrease in the light-shielding property of the cured film. SUMMARY

[0010] To overcome the problems of the prior art, the present application provides a colorant dispersion liquid having excellent storage stability, which contains a benzenesulfonic acid compound having a fluoroalkyl side chain, can effectively reduce the increase in cohesive force between colorant particles in a resin composition with time to inhibit the phenomenon of colorant flocculation. When a photosensitive resin composition containing the colorant dispersion liquid is used, the black pigment particle precipitate generated upon long-term storage can be avoided, and high light shielding properties are also obtained even upon long-term storage.

[0011] To achieve the above object, the present application provides a colorant dispersion liquid, comprising: a colorant, a dispersant, a benzenesulfonic acid compound having a fluoroalkyl side chain, and an organic solvent.

[0012] The benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structures shown in the following Formulae 4-1 to 4-12:

[0013]

[0014] Preferably, the benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structures shown in the following Formulae:

[0015]

[0016] Further, the benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structures shown in the following Formulae:

[0017]

[0018] The weight of the benzenesulfonic acid compound having a fluoroalkyl side chain is preferably 0.01 to 0.1% of the colorant.

[0019] The present application provides a photosensitive resin composition containing the above-described colorant dispersion liquid.

[0020] Further, the above-described photosensitive resin composition further contains (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) an olefinically unsaturated compound.

[0021] Further, the above-described alkali-soluble resin contains at least one of an epoxy (meth)acrylate-based resin or an acrylic copolymer resin.

[0022] The present application provides a cured product obtained by exposing, developing, and curing the above-described photosensitive resin composition.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] The colorant dispersion liquid of the present application contains a benzenesulfonic acid compound having a fluoroalkyl side chain, and by containing the benzenesulfonic acid compound having a fluoroalkyl side chain, the increase in cohesion between colorant particles in a resin composition over time can be effectively reduced to inhibit the phenomenon of colorant flocculation. In addition, the fluorine atom in the fluoroalkyl side chain in the component can significantly improve the compatibility of the colorant with the resin, the ethylenically unsaturated polymer, and the organic solvent in the photosensitive resin composition, further improve the particle size uniformity and storage stability of the colorant dispersion, avoid the generation of black pigment particle precipitates when the photosensitive resin composition is stored for a long time, and have high light shielding properties even when stored for a long time. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0026] <colorant dispersion liquid>

[0027] The present application provides a colorant dispersion liquid, comprising: a colorant, a dispersant, a benzenesulfonic acid compound having a fluoroalkyl side chain, and an organic solvent.

[0028] The colorant used in the colorant dispersion liquid of the present application is not particularly limited, and a pigment can be used, or a black dye can be used. From the durability of the cured film of the photosensitive resin composition, it is preferable to use a black pigment.

[0029] The colorant of the present application can be used alone, or two or more can be used. From the stability of the colorant dispersion liquid, it is preferable to use one colorant.

[0030] The type of colorant is not particularly limited, and for example, inorganic pigments, organic pigments can be listed. From the perspective of high impedance and low dielectric constant, an organic black pigment is preferable.

[0031] As the colorant, carbon black, perylene black, payn black, or benzofuranone-based black pigments can be listed. From the perspective of visible light shielding, insulation, infrared transmittance, and transmittance of i-line as an exposure wavelength, a benzofuranone-based black pigment is preferable, which refers to a compound represented by general formula (1), (2), or (3) or an isomer thereof. The isomer referred to here also encompasses tautomers.

[0032]

[0033] In General Formulae (1), (2), and (3), R 1 and R 2 each independently represent a hydrogen atom, a sulfonic acid group, an ester group, a carboxyl group, a cyano group, a halogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, and a or b each independently represent a positive integer of 1 to 4.

[0034] The colorant can be contained in an amount of 2 to 20% by mass based on the total amount of the photosensitive resin composition. When the colorant is contained in the above range, resolution and developability are improved.

[0035] The colorant dispersion liquid of the present application contains a dispersant. The colorant dispersant is a high molecular polymer having both a pigment-affinity group and a solvent-philic group. By containing the dispersant, the colorant can be uniformly dispersed in the organic solvent or the photosensitive resin composition of the present application, and further, the storage stability of the photosensitive resin composition is improved.

[0036] As the dispersant, polyurethane-based high molecular dispersants, polyester-based high molecular dispersants, acrylic-based high molecular dispersants, polyether-based high molecular dispersants, polyamide-based high molecular dispersants, polyallylamine-based high molecular dispersants, and polyamide-based high molecular dispersants can be exemplified.

[0037] As such a dispersant, for example, trade names EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (manufactured by BYK Corporation), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), AJISPER (registered trademark, manufactured by Ajinomoto Corporation) can be exemplified.

[0038] The dispersant used in the present application can be used alone in one kind, or two or more kinds can be used.

[0039] The content of the dispersant can be 0.1 to 10% by weight based on the total amount of the photosensitive resin composition. When the dispersant is contained in the above range, the photosensitive resin composition has excellent dispersibility, and thus has excellent stability, developability, and patterning properties when the light-shielding layer is manufactured.

[0040] The colorant dispersion liquid of the present application contains a benzene sulfonic acid compound having a fluoroalkyl side chain, and by containing the benzene sulfonic acid compound having a fluoroalkyl side chain, the increase in the cohesive force between the colorant particles in the resin composition over time can be effectively reduced to suppress the phenomenon of colorant flocculation. In addition, the fluoroalkyl side chain in the component can significantly improve the compatibility of the colorant with the resin, the ethylenically unsaturated polymer, and the organic solvent in the photosensitive resin composition, and further improve the particle size uniformity and storage stability of the colorant dispersion, and avoid the generation of black pigment particle sediments upon long-term storage.

[0041] From the perspective of ease of synthesis and cost, the benzenesulfonic acid compounds with fluorinated alkyl side chains are selected from the compounds shown in formulas 4-1 to 4-12 below:

[0042]

[0043] Furthermore, the benzenesulfonic acid compounds of the present invention having fluorinated alkyl side chains are selected from the structures shown below:

[0044]

[0045] Furthermore, the benzenesulfonic acid compounds of the present invention having fluorinated alkyl side chains are selected from the structures shown below:

[0046]

[0047] As benzenesulfonic acid compounds with fluorinated alkyl side chains, their ammonium salts can also be used.

[0048] Examples of ammonium cations that are benzenesulfonic acid compounds with fluorinated alkyl side chains include tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium.

[0049] The benzenesulfonic acid compound with fluorinated alkyl side chains in the colorant dispersion of the present invention can be one or more.

[0050] The benzenesulfonic acid compound with fluorinated alkyl side chains in this invention is 0.01-0.1% of the colorant by weight, more preferably 0.01-0.05% of the colorant by weight. When the benzenesulfonic acid compound with fluorinated alkyl side chains is 0.01% or more of the colorant by weight, it can suppress the formation of hard cake-like precipitates, and the colorant dispersion can produce a cured film with high light-blocking properties even after long-term storage. From the viewpoint of further obtaining the above-mentioned effects, it is preferable to be 0.1% or less. When a pixel segmentation layer is formed using the colorant dispersion of this invention, the breakage of the electrodes formed in the pixel segmentation layer and the charge deviation during driving are suppressed, and the light-emitting element of the organic EL display device is improved.

[0051] The colorant dispersion of the present invention contains an organic solvent that is compatible with, but does not react with, the resin, the olefinic unsaturated compound, the colorant, and the initiator. From the viewpoint of coatability and drying properties, an organic solvent with a boiling point of 100–300°C is preferred. It should be noted that the boiling point referred to herein is the boiling point at a pressure of 101.325 kPa.

[0052] Examples of organic solvents include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, and triethylene glycol. Monoethyl ether, tripropylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl Acetates, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether Ethyl ether, ethyl isobutyl ether, dihexyl ether, acetone, methyl ethyl ketone, methyl pentyle ketone, methyl isopropyl ketone, methyl isopentyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentyle ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentyle ketone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentyle alcohol, glycerol, etc.

[0053] These organic solvents can be used alone or in combination of two or more. From the perspective of ensuring good solubility of the compounded components in the photosensitive resin composition and facilitating the preparation of a photosensitive resin composition with good coatability, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methoxybutanol are preferred.

[0054] Considering the storage stability of the colorant dispersion, the content of organic solvent in the colorant dispersion is preferably 50% or more, more preferably 60% or more, and even more preferably 70% or more.

[0055] The colorant dispersion may also contain an alkali-soluble resin. Based on the total amount of the colorant dispersion, it may contain 2% to 15% by mass of alkali-soluble resin. When the amount is less than 2%, poor uniformity, poor dispersibility, and incomplete coating are likely to occur. When the amount is greater than 15%, entanglement and entanglement between resins are likely to occur, leading to an increase in colorant particle size and colorant aggregation.

[0056] <Preparation method of colorant dispersion>

[0057] Colorant dispersions can be manufactured by mixing (dispersing, kneading) components such as colorants, dispersants, benzenesulfonic acid compounds with fluorinated alkyl side chains, solvents, and other components as needed using a mixer or mixing device such as a three-roll mill, ball mill, or sand mill. The dispersions can then be filtered as needed using a filter such as a membrane filter with an aperture of about 5 μm.

[0058] After dispersing the colorant using the method described above, the concentration of the solid components of the colorant dispersion can be adjusted to the desired concentration by concentrating the obtained dispersion or diluting it with the required solvent.

[0059] <Photosensitive Resin Composition>

[0060] A second aspect of the present invention provides a photosensitive resin composition comprising the above-mentioned colorant dispersion (A).

[0061] The above-described dispersion is used as the colorant dispersion. There is no particular limitation on the amount of colorant dispersion used, as long as the photosensitive resin composition is colored with the desired hue and color concentration.

[0062] The photosensitive resin composition of the present invention further includes (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) an olefinic unsaturated compound.

[0063] As for (B) alkali-soluble resins, there are no particular limitations as long as the resin exhibits alkali solubility. Examples include resins containing carboxyl or hydroxyl groups. More specifically, examples include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, phenolic varnish resins, and polyvinylphenol resins. Especially from the viewpoint of excellent plate-making properties, the following are suitable:

[0064] (b1) Epoxy (meth)acrylate resins

[0065] (b2) Acrylic copolymer resins.

[0066] These can be used individually or in combination of two or more.

[0067] (b1) Epoxy (meth)acrylate resin is a resin obtained by reacting an epoxy compound (epoxy resin) with an α,β-unsaturated monocarboxylic acid and / or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester part, and then reacting the hydroxyl group generated therefrom with a compound having two or more substituents that can react with a polybasic acid and / or its anhydride.

[0068] Before reacting the above-mentioned polybasic acid and / or its anhydride with a hydroxyl group, a compound having two or more substituents capable of reacting with a hydroxyl group is reacted, and then the polybasic acid and / or its anhydride is reacted, the resulting resin is also included in (d1) epoxy (meth)acrylate resins.

[0069] Epoxy (meth)acrylate resins do not actually have epoxy groups in their chemical structure and are not limited to "(meth)acrylate". However, since they are made from epoxy compounds (epoxy resins) and "(meth)acrylate" is a representative example, they are named in this way by convention.

[0070] As the epoxy (meth)acrylate resin used in this invention, from the viewpoint of developability and reliability, epoxy (meth)acrylate resin (b1-1) and / or epoxy (meth)acrylate resin (b1-2) (hereinafter sometimes referred to as "carboxyl-containing epoxy (meth)acrylate resin") are suitable.

[0071] From the perspective of escaping gases, those with aromatic rings in the main chain are more suitable as (b1) epoxy (meth) acrylate resins.

[0072] <Epoxy (meth)acrylate resin (b1-1)>

[0073] An alkali-soluble resin is obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to an epoxy resin, and then reacting a polybasic acid and / or its anhydride.

[0074] <Epoxy (meth)acrylate resins (b1-2)>

[0075] An alkali-soluble resin is obtained by adding α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to an epoxy resin, and then reacting it with polyols and polyacids and / or their anhydrides.

[0076] Here, epoxy resin also includes the raw material compound that forms the resin before thermal curing, and this epoxy resin can be suitably selected from known epoxy resins. Alternatively, the epoxy resin can be a compound obtained by reacting a phenolic compound with a surface haloalcohol. As the phenolic compound, compounds with two or more phenolic hydroxyl groups are preferred, and these can be monomers or polymers.

[0077] The types of epoxy resins used as raw materials are preferably cresol varnish-type epoxy resins, phenol varnish-type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, triphenol methane type epoxy resins, biphenol varnish-type epoxy resins, naphthol varnish-type epoxy resins, epoxy resins that are products of the further reaction of dicyclopentadiene with phenol or cresol and epihaloalcohols, adamantyl alkyl-containing epoxy resins, and fluorene type epoxy resins. Those with aromatic rings in the main chain are more suitable.

[0078] As epoxy resin, epoxy resins represented by the following general formulas (B1) to (B4) are preferred. Specifically, examples include "XD-1000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B1); "NC-3000" manufactured by Nippon Kayaku Co., Ltd., which is an epoxy resin represented by the following general formula (B2); "E-201" manufactured by Osaka Organic Chemicals Co., Ltd., which is an epoxy resin represented by the following general formula (B3); and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Chemicals Co., Ltd., which is an epoxy resin represented by the following general formula (B4).

[0079]

[0080] In formula (B1), a is the average value, representing a number from 0 to 10, and R... 111 Each of these can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. It should be noted that multiple R groups present in one molecule... 111 They can be the same or different.

[0081]

[0082] In equation (B2), b1 and b2 are independent averages, representing numbers from 0 to 10, and R... 121 Each of these can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. It should be noted that multiple R groups present in one molecule... 121 They can be the same or different.

[0083]

[0084] In formula (B3), X represents the linking group shown in general formula (B3-1) or (B3-2). The molecular structure contains more than one adamantane structure, and c represents 2 or 3.

[0085]

[0086] In equations (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 Each of the following independently represents an optional adamantyl group with substituents, a hydrogen atom, an optional alkyl group with 1 to 12 carbon atoms with substituents, or an optional phenyl group with substituents; * indicates a connecting bond.

[0087]

[0088] In equation (B4), p and q each independently represent integers from 0 to 4, and R 141 and R 142 Each independently represents an alkyl or halogen atom having 1 to 4 carbon atoms, R 143 and R 144 Each of the two groups independently represents an alkylene group having 1 to 4 carbon atoms, and x and y independently represent integers greater than 0.

[0089] Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxyl group include: (meth)acrylic acid, crotonic acid, α-haloalkyl or alkoxy groups of (meth)acrylic acid; 2-(meth)acryloyloxyethyl adipic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl succinic acid, 2-(meth)acryloyloxypropyl adipic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxybutyl succinic acid, 2-(meth)acryloyloxybutyl adipic acid 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxybutylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, monomers of products obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid; or monomers obtained by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to hydroxyalkyl methacrylate or pentaerythritol tri(meth)acrylate; (meth)acrylic acid dimers. From the perspective of sensitivity, (meth)acrylic acid is preferred.

[0090] As a method for adding α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups to epoxy resin, known methods can be used. For example, α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having carboxyl groups can be reacted with epoxy resin in the presence of an esterification catalyst at a temperature of 50–150°C. Examples of esterification catalysts used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, as well as quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, benzyltrimethylammonium chloride, and dodecyltrimethylammonium chloride.

[0091] The components of epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group and esterification catalyst can be selected one by one, or two or more can be used in combination.

[0092] Regarding the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group used, it is preferably 0.5 to 1.2 equivalents relative to the epoxy group of the epoxy resin, and more preferably 0.7 to 1.1 equivalents. By using the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group at or above the aforementioned lower limit, there is a tendency to suppress insufficient introduction of unsaturated groups, and subsequent reactions with polybasic acids and / or their anhydrides are also more likely to proceed sufficiently. By setting it to the aforementioned upper limit or below, it is evident that the residue of unreacted α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters having a carboxyl group can be suppressed, and the curing properties are more likely to be improved.

[0093] Examples of polybasic acids and / or their anhydrides include, for example, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid, and their anhydrides.

[0094] The addition reaction of polybasic acids and / or their anhydrides can be carried out using known methods. The reaction can be continued under the same conditions as the addition reaction of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters with carboxyl groups to epoxy resins to obtain the target product. The amount of addition of the polybasic acid and / or its anhydride is preferably such that the acid value of the resulting carboxyl-containing epoxy (meth)acrylate resin is 10–150 mg KOH / g, more preferably 20–140 mg KOH / g. Values ​​above the lower limit tend to improve alkali developability. Values ​​below the upper limit tend to improve curing performance.

[0095] In addition reactions of polybasic acids and / or their anhydrides, polyfunctional alcohols (polyols) such as trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol can be added to introduce multibranched structures. In this case, the mixing order of the polybasic acid and / or its anhydride with the polyfunctional alcohol is not particularly restricted. By heating, the polybasic acid and / or its anhydride undergo an addition reaction with any hydroxyl group present in the reaction product of epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid esters with carboxyl groups, and a mixture of polyfunctional alcohols.

[0096] By using polyols, the molecular weight of (b1) epoxy (meth)acrylate resin can be increased, and branches can be introduced into the molecule, thus tending to achieve a balance between molecular weight and viscosity. Furthermore, the introduction rate of acid groups into the molecule can be increased, tending to easily achieve a balance between sensitivity, adhesion, etc.

[0097] The weight-average molecular weight (Mw) of the carboxyl-containing epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC), converted from polystyrene, is preferably 1000 or more, more preferably 5000 or more. Furthermore, it is preferably 30000 or less, and even more preferably 15000 or less. By setting it to the lower limit or above, the tendency for excessive solubility relative to the developer can be suppressed. By setting it to the upper limit or below, the solubility relative to the developer tends to become good.

[0098] The acid value of the carboxyl-containing epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 60 mg KOH / g or more, and even more preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. By setting the value above the lower limit, there is a tendency for improved developing solubility and better resolution. By setting the value below the upper limit, there is a tendency for better residual film yield of the photosensitive coloring composition.

[0099] The chemical structure of epoxy (meth)acrylate resins is not particularly limited. From the viewpoint of developability and reliability, epoxy (meth)acrylate resins having a partial structure shown in the following general formula (b1-I) (hereinafter sometimes simply referred to as "(b1-I) epoxy (meth)acrylate resins") and / or epoxy (meth)acrylate resins having a partial structure shown in the following general formula (b1-II) (hereinafter sometimes simply referred to as "(b1-II) epoxy (meth)acrylate resins").

[0100]

[0101] In equation (b1-I), R 11 R represents a hydrogen atom or a methyl group. 12 This indicates a divalent hydrocarbon group with optional substituents, k indicates 1 or 2, and * indicates a linking bond.

[0102] The benzene ring in formula (b1-I) may be further substituted with any substituents.

[0103]

[0104] In equation (b1-II), R 13Each can independently represent a hydrogen atom or a methyl group, R 14 R represents a divalent hydrocarbon group with a cyclic hydrocarbon group as a side chain. 15 and R 16 Each of the following independently represents a divalent aliphatic group with optional substituents, m and n independently represent integers from 0 to 2, and * represents a linking bond.

[0105] From the viewpoint of ease of synthesis, the partial structure shown in formula (b1-I) is preferably the partial structure shown in the following general formula (b1-I-1).

[0106]

[0107] In equation (b1.I.1), R 11 R 12 And k has the same meaning as in the above formula (b1-I), R X * indicates a hydrogen atom or a polybasic acid residue, and * indicates a linking bond.

[0108] The benzene ring in formula (b1-I-1) may be further substituted with any substituents.

[0109] A polybasic acid residue is a monovalent group formed by removing one OH group from a polybasic acid. Examples of polybasic acids include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, nethylenetetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0110] From the perspective of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

[0111] (b1-I) The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC), is not particularly limited, but is preferably 1000 or more, particularly preferably 4000 or more, more preferably 30000 or less, and even more preferably 15000 or less. The above-mentioned upper and lower limits can be combined arbitrarily. By setting the value above the lower limit, the residual film rate of the photosensitive coloring composition tends to become better. By setting the value below the upper limit, the solubility relative to the developing solution tends to become better.

[0112] (b1-I) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 80 mg KOH / g or more, and particularly preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. By setting the value above the lower limit, there is a tendency for improved developing solubility and better resolution. By setting the value below the upper limit, there is a tendency for better residual film yield of the photosensitive coloring composition.

[0113] The following are specific examples of (b1-I) epoxy (meth)acrylate resins. It should be noted that * in the examples indicates a linking bond.

[0114]

[0115] From the viewpoint of ensuring a tight fit to the substrate, the partial structure shown in formula (b1-II) is preferably the partial structure shown in the following general formula (b1-II-1).

[0116]

[0117] In equation (b1-II-1), R 13 R 15 R 16 , m and n have the same meaning as in equation (b1-II), R α The symbol represents a monovalent cyclic hydrocarbon group with optional substituents, p represents an integer greater than 1, and * represents a linking bond. The benzene ring in formula (b1-II-1) may be further substituted with any substituents.

[0118] From the perspective of robust film curing, R α Preferably, it is a monovalent aliphatic cyclic group, more preferably adamantyl alkyl.

[0119] The following are specific examples of some of the structures shown in formula (b1-II-1).

[0120]

[0121] From the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane, the partial structure shown in formula (b1-II) is preferably the partial structure shown in the following general formula (b1-II-2).

[0122]

[0123] In equation (b1-II-2), R 13 R 15 R 16 , m and n have the same meaning as in equation (b1-II), Rβ The symbol represents a divalent cyclic hydrocarbon group with optional substituents, and * represents a linking bond.

[0124] The benzene ring in formula (b1-II-2) may be further substituted with any substituents.

[0125] The following are specific examples of some of the structures shown in equation (b1-II-2). It should be noted that * in the examples represents a connecting key.

[0126]

[0127] From the viewpoint of coating residual film rate and patterning characteristics, the partial structure shown in formula (b1-II) is preferably the partial structure shown in the following general formula (b1-II-3).

[0128]

[0129] In equation (b1-II-3), R 13 R 14 R 15 R 16 , m and n have the same meaning as in equation (b1-II), R Z It represents a hydrogen atom or a polyacid residue.

[0130] A polybasic acid residue is a monovalent group formed by removing one OH group from a polybasic acid.

[0131] Examples of polybasic acids include: maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, methyltetrahydrophthalic acid, chlorobridged acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0132] (b1-II) The weight-average molecular weight (Mw) of the epoxy (meth)acrylate resin, as determined by gel permeation chromatography (GPC), is not particularly limited, but is preferably 1000 or more, more preferably 5000 or more. Furthermore, it is preferably 10000 or less, more preferably 7000 or less. By setting it to the lower limit or above, the residual film rate of the photosensitive coloring composition tends to be better. By setting it to the upper limit or below, the solubility relative to the developing solution tends to be better.

[0133] The acid value of the (b1-II) epoxy (meth)acrylate resin is not particularly limited, but is preferably 20 mg KOH / g or more, more preferably 40 mg KOH / g or more, and even more preferably 100 mg KOH / g or more. Furthermore, it is preferably 200 mg KOH / g or less, more preferably 120 mg KOH / g or less. The above upper and lower limits can be combined arbitrarily. By setting the value above the lower limit, there is a tendency for improved developing solubility and better resolution. By setting the value below the upper limit, there is a tendency for better residual film yield of the photosensitive coloring composition.

[0134] Carboxyl-containing epoxy (meth)acrylate resins can be used alone or in combination of two or more resins.

[0135] From the viewpoint of compatibility with colorants, dispersants, etc., (b2) acrylic copolymer resin is preferred as (B) alkali-soluble resin.

[0136] Examples of (b2) acrylic copolymer resins include copolymers of an olefinic unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b2-1)") with other olefinic unsaturated monomers that can be copolymerized (hereinafter referred to as "unsaturated monomer (b2-2)").

[0137] Examples of unsaturated monomers (b2-1) include: unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesoconic acid; mono[(meth)acryloyloxyalkyl] esters of polybasic acids with two or more members, such as succinate mono[2-(meth)acryloyloxyethyl] ester and phthalate mono[2-(meth)acryloyloxyethyl] ester; mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends, such as ω-carboxylated polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

[0138] These unsaturated monomers (b2-1) can be used alone or in combination of two or more.

[0139] Examples of unsaturated monomers (b2-2) include: N-phenylmaleimide, N-cyclohexylmaleimide, and other N-substituted maleimides; styrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether; methyl methacrylate, 2-hydroxyethyl methacrylate, allyl methacrylate, benzyl methacrylate, dicyclopentenyl methacrylate, glyceryl mono(meth)acrylate, 4-hydroxyphenyl methacrylate, ethylene oxide-modified p-cumylphenol (meth)acrylate, etc. Glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane and other (meth)acrylates; cyclohexyl vinyl ether, isobornyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane and other vinyl ethers; macromonomers with a mono(meth)acryloyl group at the end of the polymer molecular chain of polystyrene, poly(meth)acrylate, poly(n-butyl methacrylate), polysiloxane and other polymers.

[0140] These unsaturated monomers (b2-2) can be used alone or in combination of two or more.

[0141] In the copolymer of unsaturated monomer (b2-1) and unsaturated monomer (b2-2), the copolymerization ratio of unsaturated monomer (b2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By copolymerizing unsaturated monomer (b2-1) within such a range, there is a tendency to obtain a photosensitive coloring composition with excellent alkali developability and storage stability.

[0142] As (C) photopolymerization initiator, it refers to a compound that generates free radicals through irradiation by active light such as laser, ultraviolet, X-ray, electron beam, etc., including but not limited to carbazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, α-aminoalkylphenyl ketone-based photopolymerization initiators, etc. The photopolymerization initiator used in this invention may contain two or more of them.

[0143] From the perspective of improving the reaction rate during exposure and thus further suppressing development residue, oxime ester-based photopolymerization initiators are preferred. Specific examples include: BASF's "IRGACURE OXE-01" (Formula III-1) and "IRGACURE OXE-02" (Formula III-2), and Daito Chemix's DFI-091 (Formula III-3), etc.

[0144]

[0145] Based on the total amount of the photosensitive resin composition, a photopolymerization initiator can be included in an amount of 0.01 to 10% by mass or 0.01 to 5% by mass. When the initiator content is within the above range, curing will occur sufficiently during exposure in the patterning process using the photosensitive resin composition, thereby obtaining excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, as well as excellent resolution and adhesion, and preventing a decrease in transmittance due to unreacted initiator. Furthermore, the above-mentioned "photopolymerization initiator" can be used alone or in combination of two or more.

[0146] As a (D) olefinic unsaturated compound, it can be a monofunctional or polyfunctional ester of (meth)acrylic acid having at least one olefinic unsaturated double bond, which increases the crosslinking density during manufacturing and can enhance the mechanical properties of the manufactured pattern.

[0147] In this invention, it is preferred to use a polyfunctional olefin monomer having two or more olefin unsaturated groups per molecule. The number of olefin unsaturated groups in the polyfunctional olefin monomer is preferably 1 to 8, more preferably 2 to 7, and particularly preferably 3 to 6. The more olefin unsaturated groups a polyfunctional olefin monomer has, the higher its sensitivity tends to be; conversely, the fewer the olefin unsaturated groups, the higher its solubility tends to be. Examples of polyfunctional olefin monomers include: ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, 1,2,3-phenylpyrogallol triacrylate, etc.

[0148] The content of the olefinic unsaturated compound can be from 0.1% to 10% by weight relative to the total amount of the photosensitive resin composition. When the olefinic unsaturated compound is included in the above range, sufficient curing occurs during exposure in the patterning process, resulting in excellent reliability. The pattern exhibits excellent heat resistance, light resistance, and chemical resistance, as well as excellent resolution and adhesion.

[0149] (G) Other additives

[0150] In addition to the above-mentioned components, the photosensitive resin composition of the present invention may be appropriately combined with adhesion enhancers such as silane coupling agents, coatability enhancers, development modifiers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc.

[0151] (1) Adhesion enhancer

[0152] To improve adhesion to the substrate, an adhesion enhancer can be included in the photosensitive resin composition of the present invention. Preferably, silane coupling agents, phosphate-containing compounds, etc., are adhesion enhancers.

[0153] As a type of silane coupling agent, one of various silane coupling agents such as epoxy, (meth)acrylic, and amino can be used alone, or two or more can be used in combination.

[0154] As a phosphate-containing compound, phosphate esters containing (meth)acryloyl groups are preferred, such as KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.

[0155] When using an adhesion enhancer, its content is typically 0.01 to 2.0% by mass relative to the total amount in the photosensitive resin composition. When the adhesion enhancer is included within the above range, it tends to adequately improve adhesion while suppressing the tendency for decreased sensitivity and residues remaining after development to become defects.

[0156] (2) Surfactants

[0157] To improve coatability, a surfactant may be included in the photosensitive resin composition of the present invention. The surfactant may be BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-141, BYK-301, BYK-322, BYK-325, BYK-331, etc., manufactured and commercially available from BYK Chem.

[0158] It should be noted that one surfactant can be used, or two or more surfactants can be used in any combination and ratio. When using surfactants, their content is usually 0.01 to 5% by mass relative to the total amount in the photosensitive resin composition. When surfactants are included within the above range, the smoothness and uniformity of the coating film can be improved, and the deterioration of other properties can be inhibited.

[0159] <Method for manufacturing photosensitive resin composition>

[0160] Regarding the method for manufacturing the photosensitive resin composition described above, there are no particular limitations as long as the method can uniformly mix (B) the alkali-soluble resin, (C) the photopolymerization initiator, (D) the olefinic unsaturated compound, the colorant dispersion, and other optional components used as needed, in a manner that allows the concentration of the solid components of the photosensitive resin composition to be at a desired value.

[0161] <Cured film>

[0162] A third aspect of the present invention provides a cured product obtained by exposing, developing and curing the above-described photosensitive resin composition.

[0163] This invention provides a method for preparing a cured product, comprising the following steps:

[0164] Step 1: Coat the photosensitive resin composition onto the substrate to form a photosensitive resin coating, and then pre-bake it on a hot plate at 80-140℃ for 2-60 minutes to form a photosensitive film.

[0165] Step 2: Expose the above-mentioned photosensitive film using an exposure mask;

[0166] Step 3: Use an alkaline developing solution to remove the unexposed portions of the above-mentioned photosensitive film and then develop it;

[0167] Step 4: Cure the developed film at a temperature of 100℃-350℃ to obtain the cured product.

[0168] First, in step one, a photosensitive resin is coated onto a substrate to ensure a uniform thickness. Examples of substrates include substrates, silicon wafers, and substrates with a metallic coating on their surface obtained by ion sputtering or electroplating. The coating method can be dip coating, spin coating, roll coating, slot coating, spray coating, etc., and these methods can be combined. To make the coating thickness more uniform, a spin coater can be used to control the uniform film thickness, but this invention is not limited to this. Preferably, the film is formed by pre-baking, with pre-baking conditions of 80-120°C on a hot plate for 2-60 minutes.

[0169] Steps two and three are the exposure and development steps, wherein the exposure radiation is preferably at a wavelength of 190nm to 500nm, and the exposure dose is 10-5000mJ / cm. 2 .

[0170] Step four involves heat-treating the developed film in a curing oven to completely transform the composition into a heat-resistant film, thereby improving the adhesion between the patterned hardened film (hardened film) and the substrate. In this invention, the developed film is cured at a temperature of 100℃-350℃ to obtain a cured product.

[0171] <Application of Pattern Layers>

[0172] As a cured product, an example is an insulating film. When a photosensitive resin composition contains a colorant (E), a colored insulating film can be formed. In particular, when the colorant (E) is a light-blocking agent, a light-blocking insulating film can be formed.

[0173] Preferred examples of light-shielding black insulating films include the black partitions and black columnar spacers in the black matrix of panels used in various image display devices.

[0174] In addition, when the photosensitive resin composition contains a colorant (E) of color such as RGB, a cured product in the form of a colored film is formed in the area divided by the black matrix, and a color filter can be manufactured.

[0175] For example, the aforementioned black matrix and color-cured film containing color as a cured material can be appropriately used in various display devices.

[0176] Furthermore, as mentioned above, the cured product generates less gas. Therefore, the cured product formed using the photosensitive resin composition can be used as a partition wall for the light-emitting layer in an organic EL element.

[0177] The above and other advantages of the present invention can be better understood through the following embodiments, but the following embodiments are not intended to limit the scope of the present invention.

[0178] Example

[0179] The following embodiments illustrate the present invention, but the present invention is not limited to the following embodiments.

[0180] <Testing Methods>

[0181] <Evaluation of the anti-settling properties of colorant dispersions>

[0182] Within one hour of preparation, weigh 80.0 g of the prepared colorant dispersion into a 100 mL cylindrical glass bottle (3 cm bottom diameter) and seal it. Let it stand for 3 hours in a constant temperature incubator at atmospheric pressure / light protection / actual temperature 25℃±1℃, then remove and open. Scrape off the bottom of the glass bottle with a spatula to check for any black precipitate.

[0183] After storing the solution in a constant temperature chamber at atmospheric pressure / protected from light / actual temperature of 25℃±1℃ for 30 days, remove the bottle and open the cap. Invert the glass bottle for 3 minutes, apply pigment, and then filter the dispersion using a SUS filter (400 mesh). The number of black precipitates with a long diameter greater than 0.5 mm adhering to the bottom or side of the glass bottle without falling off, and the number of black precipitates with a long diameter greater than 0.5 mm retained after filtration, were used to evaluate the material on the SUS filter.

[0184] The more the formation of black precipitate is suppressed, the better. Settling resistance is evaluated according to the following criteria. If black precipitate with a major diameter greater than or equal to 2.0 mm is observed, or if black precipitate accumulates in layers on the bottom or sides of the glass bottle and cannot be counted, it should be in the form of a hard cake, producing black precipitate, and is rated as E.

[0185] A: No black precipitate was observed at all.

[0186] B: Fewer than 5 black precipitates were observed.

[0187] C: More than 5 but less than 10 black precipitates were observed.

[0188] D: Observed 10 or more black precipitates

[0189] E: A hard, cake-like black precipitate was observed.

[0190] <Evaluation of Viscosity Stability of Colorant Dispersion (Thickening Rate)>

[0191] 50g of the prepared colorant dispersion was sealed in a glass bottle within one hour of preparation and allowed to stand for 24 hours in a constant temperature incubator set at 25℃. Then, 1.0g was collected and dropped onto the platform of an E-type viscometer (cone-plate type viscometer). Shear force was applied at 50 rpm, and the viscosity observed after 3 minutes was taken as the initial viscosity (MPa·s). The viscosity after standing at 25℃ for 30 days was then measured using the same method and taken as the elapsed viscosity (MPa·s). The viscosity increase rate (%) was calculated using the following formula. A smaller absolute value of the viscosity increase rate (%) indicates better stability. The dispersion stability was evaluated based on the following criteria: A to C were considered acceptable, and D to F were considered unacceptable. In the case of sedimentation, regardless of the viscosity increase rate, the evaluation was E. When either the initial viscosity or the viscosity over time of the pigment dispersion exceeds 100 (MPa·s), it is difficult to compare and evaluate it under the same conditions because it cannot be measured. Therefore, regardless of the presence of sediment or its viscosity increase rate, it is evaluated as F.

[0192] Viscosity increase rate (%) = (Viscosity over time - Initial viscosity) / Initial viscosity × 100

[0193] A: Less than 5%

[0194] B: 5% or more but less than 10%

[0195] C: 10% or more but less than 30%

[0196] D: Over 30%

[0197] E: Sedimentation occurs

[0198] F: Viscosity too high to be measured.

[0199] <Determination of optical density per unit film thickness (unit OD value)>

[0200] The optical density per unit film thickness was measured in the following order.

[0201] First, the prepared photosensitive coloring composition was coated onto a glass substrate using a spin coater to achieve a film thickness of 2.0 μm after heat curing. After 1 minute of vacuum drying, it was dried on a hot plate at 110°C for 150 seconds. The resulting coating was then exposed without an exposure mask. An intensity of 10 mW / cm² was used as the illumination source at a wavelength of 365 nm. 2 The high-pressure mercury lamp was set to an exposure of 70 mJ / cm. 2 Next, the substrate was cured in an oven at 230°C for 30 minutes to obtain the resist-coated substrate.

[0202] The optical density (OD value) of the resist-coated substrate was measured using an X-Rite 361T(V) transmission density meter (light source color temperature: approximately 2850K (equivalent to CIE standard light source A), spectral sensitivity characteristics of the light-receiving part: ISO visual density under ISO 5-3 standard). The film thickness was measured using a VertScan(R) 2.0 non-contact surface / layer cross-sectional shape measurement system manufactured by Mitsubishi Chemical Systems Co., Ltd. The optical density (OD value) per unit film thickness (1 μm) was calculated from the OD value and film thickness. It should be noted that the OD value represents the light-blocking ability; a higher value indicates higher light-blocking performance. A smaller decrease in light-blocking performance before and after storage indicates better pigment dispersion.

[0203] The following are the components of the photosensitive resin compositions used in the examples and comparative examples.

[0204] <Alkali-soluble resin-1>

[0205] "ZCR-8035H" (weight-average molecular weight Mw = 7000, acid value = 82 mg KOH / g) manufactured by Nippon Kayaku Co., Ltd. has partial structures shown in the following general formula (C-1) and the following general formula (C-2).

[0206]

[0207] In the formula, ** represents the connecting part.

[0208] <Alkali-soluble resin-2>

[0209]

[0210] 240 parts by mass of the epoxy compound with the above structure (epoxy equivalent 264), 68.5 parts by mass of acrylic acid, 263.5 parts by mass of methoxybutyl acetate, 6.5 parts by mass of triphenylphosphine, and 0.20 parts by mass of p-methoxyphenol were placed in a flask equipped with a thermometer, a stirrer, and a condenser. The mixture was stirred and reacted at 95°C for 13 hours until the acid value became below 5 mg KOH / g.

[0211] Next, for the reaction solution obtained through the above reaction, 9.5 parts by mass of trimethylolpropane (TMP), 115.6 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), and 25.5 parts by mass of tetrahydrophthalic anhydride (THPA) were placed into a flask equipped with a thermometer, a stirrer, and a condenser. The mixture was stirred and slowly heated to 110°C to carry out the reaction, resulting in alkali-soluble resin-2 with a solid component acid value of 105 mg KOH / g and a weight-average molecular weight (Mw) of 13050 converted from polystyrene by GPC.

[0212] Colorant: Irgaphor (registered trademark) Black S 0100 CF, manufactured by BASF (with the chemical structure shown in Formula 5 below).

[0213]

[0214] Dispersant: BASF's "DISPERBYK-167"

[0215] Benzenesulfonic acid compounds with fluorinated alkyl side chains:

[0216] c-1:

[0217] c-2:

[0218] c-3:

[0219] c-4:

[0220] c-5:

[0221] Compounds c-1 to c-5 can be prepared by reacting the corresponding benzenesulfonyl chloride with water, or they can be obtained commercially.

[0222] 244.62 g of 4-(trifluoromethyl)benzenesulfonyl chloride, 1000 mL of dioxane and 1000 mL of water were added to a three-necked flask. After reflux for 6 h, the solvent was removed under reduced pressure. The compound was then recrystallized in methanol to obtain compound C1.

[0223] 260.63 g of 4-(trifluoromethoxy)benzenesulfonyl chloride, 1000 mL of dioxane and 1000 mL of water were added to a three-necked flask. After reflux for 6 h, the solvent was removed under reduced pressure. The compound C2 was obtained by recrystallization in methanol.

[0224] 258.65 g of 4-(2,2,2-trifluoroethyl)benzenesulfonyl chloride, 1000 mL of dioxane and 1000 mL of water were added to a three-necked flask. After reflux for 6 h, the solvent was removed under reduced pressure. The compound C3 was obtained by recrystallization in methanol.

[0225] Solvent 1: Propylene glycol monomethyl ether acetate (PGMEA)

[0226] Solvent 2: 3-Methoxybutanol (MB)

[0227] Photopolymerization initiator-1: An oxime ester photopolymerization initiator having the chemical structure of the following formula (6).

[0228]

[0229] Photopolymerization initiator-2: An oxime ester photopolymerization initiator having the chemical structure of the following formula (7).

[0230]

[0231] Alkene unsaturated compounds: Dipentaerythritol hexaacrylate (DPHA) produced by McLean Company

[0232] Surfactant-1: BYK-331 manufactured by BYK Corporation

[0233] Surfactant-2: BYK-141 manufactured by BYK Corporation

[0234] Adhesion enhancer additive: KAYAMER PM-21 (a phosphate ester containing methacryloyl groups), manufactured by Nippon Kayaku Co., Ltd.

[0235] <Preparation of Colorant Dispersion>

[0236] Colorant, dispersant, benzenesulfonic acid compound with fluorinated alkyl side chains, alkali-soluble resin-1, and solvent were mixed. The mixture was dispersed in a high-speed homogenizer at 0–25°C for 3 hours. The dispersed solution was then transferred to a grinder and subjected to a secondary dispersion treatment at 25–40°C for 6 hours. Zirconia beads with a diameter of 0.2 mm were used as grinding beads, as detailed in Table 1.

[0237] The amount of alkali-soluble resin-1 refers to the amount of solid components, and the amount of solvent includes the amount of solvent from the dispersant and the alkali-soluble resin.

[0238] The anti-settling and thickening properties of the prepared colorant dispersions were evaluated using the methods described above. Table 1 shows the proportions (g) of each raw material and the evaluation results.

[0239] Table 1

[0240]

[0241] <Preparation of Photosensitive Resin Composition>

[0242] Examples 1-7, Comparative Examples 1-2

[0243] The colorant dispersion, alkali-soluble resin-2, dipentaerythritol hexaacrylate (DPHA), photopolymerization initiator-1, photopolymerization initiator-2, surfactant-1 (BYK-331), surfactant-2 (BYK-141), adhesion enhancer additive (KAYAMER PM-21), propylene glycol monomethyl ether acetate, and 3-methoxybutanol were mixed and stirred to form a homogeneous solution. The solution was then filtered through an organic filter membrane with a pore size of 0.45 μm to obtain the photosensitive resin composition of the present invention.

[0244] The amount of alkali-soluble resin component is the same as the amount of solid component, and the total content of solid components in the photosensitive resin composition is 20% by mass.

[0245] The selection of raw materials and specific formulations in Examples 1-7 and Comparative Examples 1-2 are shown in Table 2. The evaluation results of the unit OD value are also shown in Table 2.

[0246] Table 2

[0247]

[0248] Although the present invention has been described in detail above with general descriptions, specific embodiments, and experiments, modifications or improvements can be made to it, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention fall within the scope of protection claimed by the present invention.

Claims

1. A colorant dispersion, characterized in that, The product comprises: a colorant, a dispersant, a benzenesulfonic acid compound having a fluorinated alkyl side chain, and an organic solvent; the colorant is selected from benzofuranone-based black pigments; the benzenesulfonic acid compound having a fluorinated alkyl side chain is selected from structures shown below: 。 2. A colorant dispersion as described in claim 1, characterized in that, The benzenesulfonic acid compounds having fluorinated alkyl side chains are selected from the structures shown below: 。 3. A colorant dispersion as described in claim 1, characterized in that, The benzenesulfonic acid compounds having fluorinated alkyl side chains are selected from the structures shown below: 。 4. A colorant dispersion as described in claim 1, characterized in that, The weight of the benzenesulfonic acid compound having a fluorinated alkyl side chain is 0.01-0.1% of the weight of the colorant.

5. A photosensitive resin composition, characterized in that, It contains a colorant dispersion as described in any one of claims 1-4.

6. A photosensitive resin composition as described in claim 5, characterized in that, The photosensitive resin composition further comprises (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) an olefinic unsaturated compound.

7. A photosensitive resin composition as described in claim 6, characterized in that, The alkali-soluble resin comprises at least one of an epoxy (meth)acrylate resin or an acrylic copolymer resin.

8. A cured product, characterized in that, It is formed by exposing, developing and curing the photosensitive resin composition according to any one of claims 5 to 7.

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