Colorant dispersion liquid, photosensitive resin composition and cured product

Abstract

The invention relates to a colorant dispersion liquid with storage stability. The colorant dispersion liquid comprises a colorant, a dispersant, a benzenesulfonic acid compound with a fluoroalkyl side chain and an organic solvent. When the photosensitive resin composition containing the colorant dispersion liquid is used, black pigment particle deposits generated at the time of long-term storage can be avoided, and the photosensitive resin composition has high light shielding properties even at the time of long-term storage.

Description

Technical Field

[0001] The present invention relates to a colorant dispersion liquid, and a negative photosensitive resin composition and a cured product produced using the same. Background Art

[0002] In recent years, OLED display devices have been rapidly popularized in terminal products such as mobile phones, electronic watches, tablet computers and personal computers due to their excellent response speed, higher brightness and contrast. As a self-luminous display device, OLED display devices have the problem of reduced visibility due to the incidence of ambient light, so it is necessary to use a polarizer to reduce the reflection of ambient light on the screen to improve the contrast and color expression of the OLED display device. However, due to the presence of the polarizer, the theoretical transmittance of the display light emitted by the OLED device is only 50%, so it is necessary to increase the luminous brightness of the OLED device to compensate for the loss of transmittance, resulting in the problem of insufficient energy efficiency of OLED.

[0003] In recent years, a technology called COE (Color Filter On Encapsulation) has emerged to reduce external light reflection from ambient light by providing a black pixel definition layer with shading properties. This technology avoids problems such as reduced light extraction efficiency caused by the use of polarizers, thereby greatly reducing the energy consumption of OLED display devices and further improving 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 mainly consists of a pigment dispersion, an alkali-soluble resin, a photopolymerization initiator, an ethylenically 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 the coloring material for blackening the pixel separation layer, it is preferred to use an organic pigment with high insulation and low dielectric constant compared to inorganic black pigments such as carbon black. However, the existing colorant dispersion is not stable enough, and there is a problem of colorant flocculation during long-term storage. Therefore, when used, it is easy to cause the colorant particle size to increase, the storage stability of the resin composition to decrease, and the light-shielding property of the cured film to decrease, which in turn leads to the problem of clogging the coating blade and reducing the light-shielding property of the cured film. Summary of the invention

[0010] In view of the shortcomings of the prior art, the present invention provides a colorant dispersion having excellent storage stability, the colorant dispersion comprising a benzenesulfonic acid compound having a fluoroalkyl side chain, which can effectively reduce the increase in cohesive force between colorant particles in a resin composition over time to inhibit the phenomenon of colorant flocculation. When a photosensitive resin composition containing the colorant dispersion is used, black pigment particle sediment generated during long-term storage can be avoided, and the composition has high light-shielding properties even during long-term storage.

[0011] To achieve the above object, the first aspect of the present invention provides a colorant dispersion 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 formulas 4-1 to 4-12:

[0013]

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

[0015]

[0016] Furthermore, the benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structure shown below:

[0017]

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

[0019] A second aspect of the present invention provides a photosensitive resin composition comprising the above-mentioned colorant dispersion.

[0020] Furthermore, the photosensitive resin composition further comprises (B) an alkali-soluble resin, (C) a photopolymerization initiator and (D) an ethylenically unsaturated compound.

[0021] Furthermore, the alkali-soluble resin at least includes one of epoxy (meth)acrylate resin and acrylic copolymer resin.

[0022] A third aspect of the present invention provides a cured product, which is obtained by exposing, developing and curing the above-mentioned photosensitive resin composition.

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

[0024] The colorant dispersion of the present invention contains a benzenesulfonic acid compound having a fluoroalkyl side chain. By containing the benzenesulfonic acid compound having a fluoroalkyl side chain, the cohesive force between the colorant particles in the resin composition can be effectively reduced to increase over time to inhibit the phenomenon of colorant flocculation. In addition, the fluorine atoms in the fluoroalkyl side chains in the components can significantly improve the compatibility of the colorant with the resin, ethylenically unsaturated polymer and organic solvent in the photosensitive resin composition, thereby improving the particle size uniformity and storage stability of the colorant dispersion, avoiding the black pigment particle sediment generated when the photosensitive resin composition is stored for a long time, and having high light-shielding properties even when stored for a long time. DETAILED DESCRIPTION

[0025] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] <Colorant Dispersion>

[0027] The first aspect of the present invention 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 of the present invention is not particularly limited, and a pigment or a black dye may be used. From the perspective of durability of the cured film of the photosensitive resin composition, a black pigment is preferably used.

[0029] The colorant of the present invention may be used alone or in combination of two or more. From the perspective of the stability of the colorant dispersion, it is preferred to use a single colorant.

[0030] The type of colorant is not particularly limited, and examples thereof include inorganic pigments and organic pigments. Organic black pigments are preferred from the viewpoint of high impedance and low dielectric constant.

[0031] As colorants, carbon black, perylene black, black or benzofuranone-based black pigments can be cited. From the perspective of visible light shielding, insulation, infrared transmittance and transmittance of i-line as exposure wavelength, benzofuranone-based black pigments are preferred, and the benzofuranone-based black pigment refers to a compound represented by general formula (1), (2) or (3) or an isomer thereof. The so-called isomers herein also include tautomers.

[0032]

[0033] In the general formulas (1), (2) and (3), R 1 and R 2 Each independently represents 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 represents a positive integer of 1 to 4.

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

[0035] The colorant dispersion of the present invention contains a dispersant. The colorant dispersant is a high molecular polymer having both a pigment affinity group and a solvent affinity group. By containing a dispersant, the colorant can be uniformly dispersed in an organic solvent or the photosensitive resin composition of the present invention, thereby improving the storage stability of the photosensitive resin composition.

[0036] Examples of the dispersant include polyurethane-based polymer dispersants, polyester-based polymer dispersants, acrylic-based polymer dispersants, polyether-based polymer dispersants, polyamide-based polymer dispersants, polyallylamine-based polymer dispersants, and polyamide-based polymer dispersants.

[0037] Examples of such dispersants include trade names EFKA (registered trademark, manufactured by BASF), DISPERBYK (manufactured by BYK), SOLSPERSE (registered trademark, manufactured by Lubrizol), and AJISPER (registered trademark, manufactured by Ajinomoto Co., Ltd.).

[0038] The dispersant used in the present invention may be used alone or in combination of two or more.

[0039] The dispersant may be included in an amount of 0.1 to 10 wt % based on the total amount of the photosensitive resin composition. When the dispersant is included within the above range, the photosensitive resin composition has excellent dispersibility and thus has excellent stability, developability, and patternability when manufacturing a light shielding layer.

[0040] The colorant dispersion of the present invention contains a benzenesulfonic acid compound having a fluoroalkyl side chain. By containing the benzenesulfonic acid compound having a fluoroalkyl side chain, the cohesive force between the colorant particles in the resin composition can be effectively reduced to increase over time to inhibit 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, ethylenically unsaturated polymer and organic solvent in the photosensitive resin composition, thereby improving the particle size uniformity and storage stability of the colorant dispersion, and avoiding the generation of black pigment particle sediments during long-term storage.

[0041] From the perspective of ease of synthesis and cost, the benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the compounds shown in the following formulas 4-1 to 4-12:

[0042]

[0043] Furthermore, the benzenesulfonic acid compound having a fluoroalkyl side chain of the present invention is selected from the structure shown below:

[0044]

[0045] Furthermore, the benzenesulfonic acid compound having a fluoroalkyl side chain of the present invention is selected from the structure shown below:

[0046]

[0047] As the benzenesulfonic acid compound having a fluoroalkyl side chain, an ammonium salt thereof may also be used.

[0048] Examples of the ammonium cation of the benzenesulfonic acid compound having a fluoroalkyl side chain include tetramethylammonium, tetraethylammonium, tetrabutylammonium, and trimethylbenzylammonium.

[0049] The benzenesulfonic acid compound having a fluoroalkyl side chain in the colorant dispersion of the present invention may be used alone or in combination of two or more.

[0050] Relative to the weight of the colorant, the weight of the benzenesulfonic acid compound with a fluoroalkyl side chain in the present invention is 0.01-0.1% of the colorant, and more preferably 0.01-0.05% of the weight of the colorant. When the benzenesulfonic acid compound with a fluoroalkyl side chain is 0.01% or more relative to the weight of the colorant, the effect of suppressing the appearance of hard cake-like precipitates can be obtained, and the colorant dispersion can be a cured film with high light-shielding properties even after long-term storage. From the viewpoint of further obtaining the above-mentioned effects, it is preferably 0.1% or less. When the colorant dispersion of the present invention is used to form a pixel segmentation layer, the disconnection of the electrode 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, which is compatible with the resin, the ethylenically unsaturated compound, the colorant and the initiator but does not react. Among the organic solvents, an organic solvent having a boiling point of 100 to 300° C. is preferably selected from the viewpoints of coating and drying properties. It should be noted that the boiling point referred to here refers to the boiling point under a pressure of 101.325 kPa.

[0052] Examples of the organic solvent 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, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether. 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, ethylene glycol monomethyl 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 Acetate, 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, amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl amyl ketone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl amyl alcohol, glycerol, etc.

[0053] These organic solvents may be used alone or in combination of two or more thereof. From the perspective of dissolving the formulated components well in the photosensitive resin composition and facilitating the preparation of a photosensitive resin composition having good coating properties, 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] From the viewpoint of storage stability of the colorant dispersion, the content of the organic solvent is preferably 50% or more, more preferably 60% or more, and further preferably 70% or more, based on the colorant dispersion.

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

[0056] <Method for producing colorant dispersion>

[0057] The colorant dispersion can be prepared by mixing (dispersing, kneading) the colorant, dispersant, benzenesulfonic acid compound having a fluoroalkyl side chain, solvent and other components as needed using a stirrer or kneading device such as a three-roll mill, a ball mill or a sand mill, and filtering with a filter such as a membrane filter having a caliber of about 5 μm as needed.

[0058] After the colorant is dispersed as described above, the solid content concentration of the colorant dispersion can be adjusted to a desired concentration by concentrating the obtained dispersion or diluting it with a desired solvent.

[0059] <Photosensitive resin composition>

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

[0061] As the colorant dispersion, the above-mentioned dispersion is used. The amount of the colorant dispersion used is not particularly limited as long as the photosensitive resin composition is colored with a desired color tone and color density.

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

[0063] The alkali-soluble resin (B) is not particularly limited as long as it is a resin that exhibits alkali solubility, and examples thereof include resins containing a carboxyl group or a hydroxyl group, and more specifically, examples thereof include epoxy (meth)acrylate resins, acrylic resins, carboxyl-containing epoxy resins, carboxyl-containing urethane resins, novolac resins, and polyvinylphenol resins. In particular, from the viewpoint of excellent platemaking properties, the following are preferably used:

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

[0065] (b2) Acrylic copolymer resin.

[0066] These can be used individually by 1 type or in combination of 2 or more types.

[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 portion, wherein the hydroxyl group generated by the reaction is further reacted with a compound having two or more substituents capable of reacting with the hydroxyl group, such as a polyacid and / or its anhydride.

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

[0069] Epoxy (meth)acrylate resins do not substantially have epoxy groups in their chemical structures and are not limited to "(meth)acrylates". However, since they are made from epoxy compounds (epoxy resins) and are represented by "(meth)acrylates", they are named as such according to custom.

[0070] As the (b1) epoxy (meth)acrylate resin used in the present 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 group-containing epoxy (meth)acrylate resin") are preferably used.

[0071] As the (b1) epoxy (meth)acrylate resin, those having an aromatic ring in the main chain can be more preferably used from the viewpoint of outgassing.

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

[0073] An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin and further reacting a polybasic acid and / or an anhydride thereof.

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

[0075] An alkali-soluble resin obtained by adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, and then reacting the epoxy resin with a polyol and a polybasic acid and / or an anhydride thereof.

[0076] Here, epoxy resin also comprises the raw material compound before forming resin by thermosetting, and as this epoxy resin, can suitably select to use from known epoxy resin.In addition, epoxy resin can use the compound obtained by phenolic compound and epihalohydrin reaction.As phenolic compound, preferably 2 yuan or 2 yuan or more compound with phenolic hydroxyl group, can be monomer or can be polymer.

[0077] As the type of epoxy resin that becomes the raw material, for example, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, an epoxy resin that is a reaction product of a polyaddition reaction product of dicyclopentadiene and phenol or cresol and further with an epihalohydrin, an adamantyl-containing epoxy resin, and a fluorene-type epoxy resin can be preferably used, and those having an aromatic ring in the main chain can be more preferably used.

[0078] As the epoxy resin, the epoxy resin represented by the following general formula (B1) to (B4) can be preferably used. Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B1), "NC-3000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (B2), "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as the epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nippon Steel & Sumigin Chemical Co., Ltd. as the epoxy resin represented by the following general formula (B4).

[0079]

[0080] In formula (B1), a is an average value, representing a number from 0 to 10, and R 111 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. 111 They may be the same or different, respectively.

[0081]

[0082] In formula (B2), b1 and b2 are each independently an average value and represent a number from 0 to 10, and R 121 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. 121 They may be the same or different, respectively.

[0083]

[0084] In formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2): wherein the molecular structure contains one or more adamantane structures, and c represents 2 or 3.

[0085]

[0086] In formula (B3-1) and (B3-2), R 131 ~R 134 and R 135 ~R 137 Each independently represents an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, and * represents a bond.

[0087]

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

[0089] Examples of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include: (meth)acrylic acid, crotonic acid, α-halogenated alkyl and 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)acryloyloxybutyl hydrogenphthalic acid, 2-(meth)acryloyloxybutylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, a monomer of a product obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth)acrylic acid; or a monomer obtained by adding acids (anhydrides) such as succinic acid (anhydride), phthalic acid (anhydride), and maleic acid (anhydride) to hydroxyalkyl (meth)acrylate and pentaerythritol tri(meth)acrylate; (meth)acrylic acid dimer. From the viewpoint of sensitivity, (meth)acrylic acid is preferred.

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

[0091] The epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two or more.

[0092] The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used is preferably 0.5 to 1.2 equivalents, and more preferably 0.7 to 1.1 equivalents, relative to 1 equivalent of epoxy group of the epoxy resin. By making the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group used more than the above lower limit, there is a tendency to suppress the insufficient amount of unsaturated group introduction, and the subsequent reaction with the polyacid and / or its anhydride is also easy to proceed fully. By setting it below the above upper limit, it can be seen that the residual unreacted product of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group can be suppressed, and the curing characteristics tend to be good.

[0093] Examples of the polybasic acid and / or its anhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

[0094] The addition reaction of the polyacid and / or its anhydride can be carried out using a known method, and the target product can be obtained by continuing the reaction under the same conditions as the addition reaction of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to epoxy resin. The addition amount of the polyacid and / or its anhydride component is preferably such that the acid value of the generated carboxyl-containing epoxy (meth) acrylate resin is 10 to 150 mg KOH / g, and more preferably 20 to 140 mg KOH / g. By being above the above lower limit, there is a tendency for alkali developability to become good. By being below the above upper limit, there is a tendency for curing performance to become good.

[0095] In the addition reaction of the polyacid and / or its anhydride, a polyfunctional alcohol (polyol) such as trimethylolpropane, di(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3-propanetriol, etc. can be added to introduce a multi-branched structure. In this case, there is no particular restriction on the mixing order of the polyacid and / or its anhydride and the polyfunctional alcohol. By heating, the polyacid and / or its anhydride react with any hydroxyl group present in the reaction product of the epoxy resin and the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the mixture of the polyfunctional alcohol.

[0096] By using a polyol, the molecular weight of the epoxy (meth)acrylate resin (b1) can be increased, and branches can be introduced into the molecule, thereby tending to achieve a balance between molecular weight and viscosity. In addition, 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 measured by gel permeation chromatography (GPC) in terms of polystyrene is preferably 1000 or more, more preferably 5000 or more. In addition, it is preferably 30000 or less, and more preferably 15000 or less. By setting it to above the lower limit, there is a tendency that the solubility with respect to the developer becomes excessively high. By setting it to below the upper limit, there is a tendency that the solubility with respect 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 mgKOH / g or more, more preferably 60 mgKOH / g or more, and even more preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. By setting it to the above lower limit value or more, there is a tendency that the developing solubility is improved and the resolution becomes good. By setting it to the above upper limit value or less, there is a tendency that the residual film rate of the photosensitive coloring composition becomes good.

[0099] The chemical structure of the epoxy (meth)acrylate resin is not particularly limited. From the viewpoint of developability and reliability, it is preferred to contain an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (b1-I) (hereinafter sometimes referred to as "(b1-I) epoxy (meth)acrylate resin"). and / or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (b1-II) (hereinafter sometimes referred to as "(b1-II) epoxy (meth)acrylate resin").

[0100]

[0101] In formula (b1-I), R 11 represents a hydrogen atom or a methyl group, R 12 represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a connecting bond.

[0102] The benzene ring in the formula (b1-I) may be further substituted by any substituent.

[0103]

[0104] In formula (b1-II), R 13Each independently represents a hydrogen atom or a methyl group, R 14 represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, R 15 and R 16 Each independently represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a connecting bond.

[0105] From the viewpoint of simplicity of synthesis, the partial structure represented by formula (b1-I) is preferably a partial structure represented by the following general formula (b1-I-1).

[0106]

[0107] In formula (b1.I.1), R 11 , R 12 and k have the same meanings as in the above formula (b1-I), R X represents a hydrogen atom or a polyacid residue, and * represents a connecting bond.

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

[0109] The polyacid residue refers to a monovalent group formed by removing one OH group from a polyacid. Examples of the polyacid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0110] From the viewpoint 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 measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, particularly preferably 4000 or more, preferably 30000 or less, and further preferably 15000 or less. The above upper and lower limits may be combined arbitrarily. By setting it to above the above lower limit, there is a tendency for the residual film rate of the photosensitive coloring composition to become good. By setting it to below the above upper limit, there is a tendency for the solubility in the developer to become good.

[0112] (b1-I) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 80 mgKOH / g or more, and particularly preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, and particularly preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. By setting it to above the above lower limit, there is a tendency that the developing solubility is improved and the resolution becomes good. By setting it to below the above upper limit, there is a tendency that the residual film rate of the photosensitive coloring composition becomes good.

[0113] Specific examples of (b1-I) epoxy (meth)acrylate resins are listed below. In addition, * in the examples represents a connecting bond.

[0114]

[0115] From the viewpoint of adhesion to the substrate, the partial structure represented by formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1).

[0116]

[0117] In formula (b1-II-1), R 13 , R 15 , R 16 , m and n have the same meanings as in formula (b1-II), R α represents a monovalent cyclic hydrocarbon group which may have a substituent, p represents an integer greater than or equal to 1, and * represents a connecting bond. The benzene ring in the formula (b1-II-1) may be further substituted by an arbitrary substituent.

[0118] From the perspective of a strong film cure, R α It is preferably a monovalent aliphatic ring group, and more preferably an adamantyl group.

[0119] Specific examples of the partial structure represented by formula (b1-II-1) are listed below.

[0120]

[0121] From the viewpoint of the rigidity of the skeleton and the hydrophobization of the membrane, the partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2).

[0122]

[0123] In formula (b1-II-2), R 13 , R 15 , R 16 , m and n have the same meanings as in formula (b1-II), Rβ represents a divalent cyclic hydrocarbon group which may have a substituent, and * represents a connecting bond.

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

[0125] Specific examples of the partial structure represented by formula (b1-II-2) are listed below. It should be noted that * in the examples represents a connecting bond.

[0126]

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

[0128]

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

[0130] The polybasic acid residue refers to a monovalent group formed by removing one OH group from a polybasic acid.

[0131] Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorobridgeic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

[0132] The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (b1-II) measured by gel permeation chromatography (GPC) in terms of polystyrene is not particularly limited, but is preferably 1000 or more, more preferably 5000 or more. In addition, it is preferably 10000 or less, more preferably 7000 or less. By setting it to be above the above lower limit, there is a tendency for the residual film rate of the photosensitive coloring composition to become good. By setting it to be below the above upper limit, there is a tendency for the solubility in the developer to become good.

[0133] (b1-II) The acid value of the epoxy (meth) acrylate resin is not particularly limited, but is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, and further preferably 100 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, and more preferably 120 mgKOH / g or less. The above upper and lower limits may be combined arbitrarily. By setting it to above the above lower limit, there is a tendency that the developing solubility is improved and the resolution becomes good. By setting it to below the above upper limit, there is a tendency that the residual film rate of the photosensitive coloring composition becomes good.

[0134] The carboxyl group-containing epoxy (meth)acrylate resin may be used alone or in combination of two or more.

[0135] As the (B) alkali-soluble resin, it is preferred to use (b2) an acrylic copolymer resin from the viewpoint of compatibility with a colorant, a dispersant, and the like.

[0136] Examples of the (b2) acrylic copolymer resin include copolymers of an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b2-1)”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “unsaturated monomer (b2-2)”).

[0137] As the unsaturated monomer (b2-1), for example: 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 mesaconic acid; mono (meth)acryloxyalkyl esters of polybasic acids with a valence of 2 or more, such as mono (2-(meth)acryloxyethyl) succinate and mono (2-(meth)acryloxyethyl) phthalate; mono (meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxy 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 the unsaturated monomer (b2-2) include: N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether; methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, ethylene oxide-modified (meth)acrylate of p-cumylphenol, (meth)acrylate; (Meth)acrylates such as glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-〔(meth)acryloyloxymethyl〕oxetane, 3-〔(meth)acryloyloxymethyl〕-3-ethyloxetane; vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane; macromonomers having a mono(meth)acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, polysiloxane, etc.

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

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

[0142] (C) Photopolymerization initiator refers to a compound that generates free radicals by irradiation with active light such as laser, ultraviolet light, 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-aminoalkylphenone-based photopolymerization initiators, etc. The photopolymerization initiator used in the present invention may contain two or more of them.

[0143] From the viewpoint of increasing the reaction rate during exposure and thus being able to further suppress the development residue, the photopolymerization initiator is preferably an oxime ester-based photopolymerization initiator, and specific examples thereof include "IRGACURE OXE-01" (Formula III-1), "IRGACURE OXE-02" (Formula III-2) produced by BASF, and DFI-091 (Formula III-3) produced by Daito Chemix.

[0144]

[0145] The photopolymerization initiator may be included in an amount of 0.01 to 10% by mass or 0.01 to 5% by mass based on the total amount of the photosensitive resin composition. When the content of the initiator is within the above range, curing occurs sufficiently during the exposure process in the pattern forming process using the photosensitive resin composition, thereby obtaining excellent reliability, excellent heat resistance, light resistance and chemical resistance of the pattern, and excellent resolution and adhesion, and can prevent the reduction of transmittance due to unreacted initiator. In addition, the above "photopolymerization initiator" can be used alone or in combination of two or more.

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

[0147] In the present invention, it is preferred to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule, and the number of ethylenic unsaturated groups possessed by the polyfunctional ethylenic monomer is preferably 1 to 8, more preferably 2 to 7, and particularly preferably 3 to 6. The more ethylenic unsaturated groups a polyfunctional ethylenic monomer has, the higher the sensitivity tends to be, and vice versa, the lower the number of ethylenic unsaturated groups tends to be, the higher the solubility tends to be. Examples of the multifunctional olefinic monomer include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and 1,2,3-benzenetriol triacrylate.

[0148] The content of the ethylenically unsaturated compound may be 0.1 wt % to 10 wt % relative to the total amount of the photosensitive resin composition. When the ethylenically unsaturated compound is included within the above range, hardening occurs sufficiently during exposure during pattern formation, reliability is excellent, and the pattern has excellent heat resistance, light resistance, and chemical resistance, and also has excellent resolution and adhesion.

[0149] (G) Other additives

[0150] The photosensitive resin composition of the present invention may contain, in addition to the above-mentioned components, an adhesion improver such as a silane coupling agent, a coating property improver, a development improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like.

[0151] (1) Adhesion enhancer

[0152] The photosensitive resin composition of the present invention may contain an adhesion improver in order to improve adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound, and the like are preferred.

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

[0154] As the phosphoric acid group-containing compound, phosphoric acid esters containing a (meth)acryloyl group are preferred, for example, KAYAMER PM-21 manufactured by Nippon Kayaku Co., Ltd.

[0155] When an adhesion enhancer is used, its content is usually 0.01 to 2.0% by mass relative to the total amount in the photosensitive resin composition. When the adhesion enhancer is contained within the above range, the adhesion enhancing effect tends to be sufficiently obtained while reducing the sensitivity and preventing residues from remaining after development and becoming defects.

[0156] (2) Surfactants

[0157] In order to improve the coating property, the photosensitive resin composition of the present invention may also contain a surfactant. 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., which are manufactured by BYK Chem and are commercially available.

[0158] It should be noted that the surfactant can be used alone or in any combination and ratio. When a surfactant is used, its content is usually 0.01 to 5% by mass relative to the total amount in the photosensitive resin composition. When the surfactant is included in the above range, the smoothness and uniformity of the coating can be improved, and the deterioration of other characteristics can be suppressed.

[0159] <Method for producing photosensitive resin composition>

[0160] The method for producing the photosensitive resin composition described above is not particularly limited as long as it is a method that can uniformly mix (B) an alkali-soluble resin, (C) a photopolymerization initiator, (D) an ethylenically unsaturated compound, a colorant dispersion, and other optional components used as needed so that the solid content concentration of the photosensitive resin composition becomes 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 photosensitive resin composition.

[0163] The present invention provides a method for preparing a solidified material, which comprises the following steps:

[0164] Step 1: coating the photosensitive resin composition on the substrate to form a photosensitive resin coating, and then pre-baking on a hot plate at 80-140° C. for 2-60 minutes to form a photosensitive film;

[0165] Step 2: using an exposure mask to expose the photosensitive film;

[0166] Step 3: removing the unexposed portion of the photosensitive film using an alkaline developer and developing the film;

[0167] Step 4: Curing the developed film at a temperature of 100° C. to 350° C. to obtain a cured product.

[0168] First, in step 1, a photosensitive resin is coated on a substrate to make it uniform in thickness. Examples of substrates may include substrates, silicon wafers, substrates with a metal coating on the surface by ion sputtering or electroplating, etc.; the coating method may be dip coating, spin coating, roller coating, slit coating, spray coating, etc., and these methods may be combined; in order to make the coating thickness more uniform, the present invention may use a coating machine to control the uniform film thickness, but is not limited thereto. It is preferred to form the film by pre-baking, and the pre-baking conditions are pre-baking on a hot plate at 80-120°C for 2-60 minutes.

[0169] Steps 2 and 3 are exposure and development steps, wherein the exposure radiation preferably has a wavelength of 190nm to 500nm and an exposure dose of 10-5000mJ / cm 2 .

[0170] Step 4: heat-treating the developed film in a curing furnace to completely convert the composition into a heat-resistant film, thereby improving the adhesion between the patterned hardened film (hardened film) and the substrate. In the present invention, the developed film is cured at a temperature of 100° C. to 350° C. to obtain a cured product.

[0171] <Application of pattern layer>

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

[0173] Preferred examples of the light-shielding black insulating film include black partition walls and black columnar spacers in a black matrix included in panels for various image display devices.

[0174] Moreover, when the photosensitive resin composition contains a coloring agent (E) of a color such as RGB, a cured product in the form of a colored film is formed in the regions partitioned by the black matrix, and a color filter can be produced.

[0175] For example, the above-mentioned black matrix and color filter including a colored cured film as a cured product can be suitably used in various display devices.

[0176] In addition, as described above, the gas generated by the cured product is small. Therefore, the cured product formed using the photosensitive resin composition can be used as a partition wall for partitioning the light-emitting layer in an organic EL device.

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

[0178] Example

[0179] The present invention is described below with reference to the following examples, but the present invention is not limited to the following examples.

[0180] <Test Method>

[0181] <Evaluation of Anti-Settling Property of Colorant Dispersion>

[0182] Within 1 hour after preparation, weigh 80.0 g of the prepared colorant dispersion into a 100 mL cylindrical glass bottle container (bottom diameter 3 cm), seal it. Leave it in a thermostat at normal pressure / light shielding / actual temperature 25°C ± 1°C for 3 hours, take it out and unseal it. Scrape the bottom of the glass bottle container with a scraper to check whether there is any black precipitate.

[0183] After being stored in a thermostat at normal pressure / light-proof / actual temperature of 25℃±1℃ for 30 days, the lid was removed and opened, the glass bottle container was inverted for 3 minutes, the pigment was applied, and the dispersion was filtered through a SUS filter (400 mesh). The number of black precipitates with a long diameter of 0.5mm or more attached to the bottom or side of the glass bottle container without falling, and the number of black precipitates with a long diameter of 0.5mm or more retained after filtration evaluated the material on the SUS filter.

[0184] The more the generation of black precipitate is suppressed, the better. The sedimentation resistance is evaluated according to the following criteria. If a black precipitate with a major diameter greater than or equal to 2.0 mm is observed, or the black precipitate is accumulated in layers at the bottom or side of the glass bottle container and cannot be counted, it should be in the form of a hard cake, and black precipitate is generated, and the evaluation is E.

[0185] A: No black precipitate was observed

[0186] B: Less than 5 black precipitates were observed

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

[0188] D: 10 or more black precipitates were observed

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

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

[0191] The colorant dispersion prepared by 50g is sealed in a glass bottle within 1 hour after preparation, and is allowed to stand in a thermostat set at 25°C for 24 hours, and then 1.0g is collected and added dropwise to the platform of an E-type viscometer (vertebral plate viscometer), and a shear force is applied under the condition of a rotation speed of 50rpm. The viscosity displayed after 3 minutes is taken as the initial viscosity (mPa·s). The viscosity after standing at 25°C for 30 days is then measured by the same method, and it is taken as the viscosity over time (mPa·s), and the viscosity increase rate (%) is calculated according to the following formula. The smaller the absolute value of the viscosity increase rate (%), the better the stability. The dispersion stability is evaluated based on the following judgment criteria, and A~C is qualified and D~F is unqualified. Among them, in the case of sedimentation, regardless of the viscosity increase rate, it is evaluated as E. When either the initial viscosity or the viscosity over time of the pigment dispersion exceeded 100 (mPa·s), it was difficult to compare and evaluate under the same conditions because it could not be measured. Therefore, the dispersion was evaluated as F regardless of the presence or absence of sedimentation and the viscosity increase ratio.

[0192] Thickening rate (%) = (time-dependent viscosity - initial viscosity) / initial viscosity × 100

[0193] A: Less than 5%

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

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

[0196] D: 30% or more

[0197] E: Produce sediment

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

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

[0200] The optical density per unit film thickness was measured according to the following procedure.

[0201] First, the prepared photosensitive coloring composition was applied to a glass substrate using a spin coater so that the film thickness after heat curing was 2.0 μm, and then dried under reduced pressure for 1 minute, and then dried for 150 seconds at 110°C using a hot plate. The obtained coating was exposed without using an exposure mask. As the irradiation light source, a wavelength of 365 nm with an intensity of 10 mW / cm 2 The exposure was set to 70 mJ / cm 2 Next, the resultant was cured by heating in an oven at 230° C. for 30 minutes, thereby obtaining a resist-coated substrate.

[0202] The optical density (OD value) of the obtained resist-coated substrate was measured using a 361T(V) transmission densitometer manufactured by X-Rite (color temperature of the illumination light source: about 2850K (equivalent to CIE standard light source A), spectral sensitivity characteristics of the light receiving part: ISO visual density under ISO5-3 standard), and the film thickness was measured using the non-contact surface / layer cross-sectional shape measurement system VertScan(R)2.0 manufactured by Ryoka Systems Co., Ltd. The optical density (OD value per unit film thickness (1 μm) was calculated from the optical density (OD value) and the film thickness. It should be noted that the OD value is a numerical value indicating the light-shielding ability, and the larger the value, the higher the light-shielding property. The smaller the decrease in light-shielding property before and after storage, the better the pigment dispersion.

[0203] The following are the constituent components of the photosensitive resin composition used in Examples and Comparative Examples.

[0204] <Alkali soluble resin-1>

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

[0206]

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

[0208] <Alkali soluble resin-2>

[0209]

[0210] 240 parts by mass of the epoxy compound (epoxy equivalent 264) of the above structure, 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, and reacted at 95° C. for 13 hours while stirring until the acid value became less than 5 mgKOH / g.

[0211] Next, for the reaction liquid obtained by the above reaction, 9.5 parts by mass of trimethylolpropane (TMP), 115.6 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 25.5 parts by mass of tetrahydrophthalic anhydride (THPA) were put into a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was slowly raised to 110°C while stirring to carry out a reaction, thereby obtaining an alkali-soluble resin-2 having a solid acid value of 105 mgKOH / g and a weight average molecular weight (Mw) of 13050 in terms of polystyrene measured by GPC.

[0212] Colorant: Irgaphor (registered trademark) Black S 0100 CF manufactured by BASF (having the chemical structure shown in the following formula 5)

[0213]

[0214] Dispersant: "DISPERBYK-167" manufactured by BASF

[0215] Benzenesulfonic acid compounds with fluoroalkyl 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 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 reaction for 6 h, the solvent was removed under reduced pressure and recrystallized from methanol to obtain compound C1.

[0223] Add 260.63 g of 4-(trifluoromethoxy)benzenesulfonyl chloride, 1000 mL of dioxane and 1000 mL of water into a three-necked flask, reflux for 6 h, remove the solvent under reduced pressure, and recrystallize from methanol to obtain compound C2.

[0224] Add 258.65 g of 4-(2,2,2-trifluoroethyl)benzenesulfonyl chloride, 1000 mL of dioxane and 1000 mL of water into a three-necked flask, reflux for 6 h, remove the solvent under reduced pressure, and recrystallize from methanol to obtain compound C3.

[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: Oxime ester photopolymerization initiator having the chemical structure of the following formula (7)

[0230]

[0231] Olefinic unsaturated compound: Dipentaerythritol hexaacrylate DPHA manufactured by MacLean

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

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

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

[0235] <Preparation of Colorant Dispersion>

[0236] The colorant, dispersant, benzenesulfonic acid compound having a fluoroalkyl side chain, alkali-soluble resin-1 and solvent were mixed, and the mixed solution was dispersed at 0-25°C for 3 hours using a high-speed homogenizer, and then the dispersed solution was transferred to a grinder and subjected to secondary dispersion treatment at 25-40°C for 6 hours. As grinding beads, zirconia beads with a diameter of 0.2 mm were used, as shown in Table 1.

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

[0238] The prepared colorant dispersion was evaluated for its anti-sedimentation property and viscosity increase ratio by the above-mentioned method. Table 1 shows the blending amount (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] A colorant dispersion, an alkali-soluble resin-2, an olefinically unsaturated compound dipentaerythritol hexaacrylate DPHA, a photopolymerization initiator-1, a photopolymerization initiator-2, a surfactant-1 BYK-331, a surfactant-2 BYK-141, a close-fitting agent additive KAYAMER PM-21, propylene glycol monomethyl ether acetate, and 3-methoxybutanol are mixed and stirred to form a uniform solution, and filtered using 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 the alkali-soluble resin component used is the amount of the solid content, and the content ratio of the total solid content in the photosensitive resin composition is 20% by mass.

[0245] The selection and specific formulation of raw materials in Examples 1-7 and Comparative Examples 1-2 are shown in Table 2, and the evaluation results of the unit OD values ​​are shown in Table 2.

[0246] Table 2

[0247]

[0248] Although the present invention has been described in detail above by means of general description, specific implementation methods and tests, it is obvious to those skilled in the art that some modifications or improvements may be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A colorant dispersion, characterized in that: The invention comprises: a colorant, a dispersant, a benzenesulfonic acid compound having a fluoroalkyl side chain and an organic solvent.

2. A colorant dispersion according to claim 1, characterized in that: The benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structures shown in the following formulas 4-1 to 4-12:

3. A colorant dispersion according to claim 1 or 2, characterized in that: The benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structure shown below:

4. A colorant dispersion according to claim 1 or 2, characterized in that: The benzenesulfonic acid compound having a fluoroalkyl side chain is selected from the structure shown below:

5. A colorant dispersion according to claim 1 or 2, characterized in that: The weight of the benzenesulfonic acid compound having a fluoroalkyl side chain is preferably 0.01-0.1% of the colorant.

6. A photosensitive resin composition, characterized in that: A dispersion containing the colorant as claimed in claims 1 to 3.

7. A photosensitive resin composition as claimed in claim 4, characterized in that: The photosensitive resin composition further includes (B) an alkali-soluble resin, (C) a photopolymerization initiator, and (D) an ethylenically unsaturated compound.

8. A photosensitive resin composition as claimed in claim 7, characterized in that: The alkali-soluble resin includes at least one of epoxy (meth)acrylate resin and acrylic copolymer resin.

9. A solidified product, characterized in that: The photosensitive resin composition according to any one of claims 6 to 8 is exposed, developed and cured.

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