Black pigment liquid and preparation method thereof, photoresist composition, photosensitive glass and liquid crystal display device

Abstract

The invention provides a black pigment liquid and a preparation method thereof, a photoresist composition, photosensitive glass and a liquid crystal display device, and relates to the field of liquid crystal display devices. The raw material of the black pigment liquid comprises modified carbon black; the modified carbon black comprises carbon black and a coating layer coating the carbon black; the coating layer comprises a dopamine polymer. The black pigment liquid provided by the invention is high in impedance and excellent in storage stability.

Description

Technical Field

[0001] The present application relates to the field of liquid crystal display devices, and in particular to a black pigment liquid and a preparation method thereof, a photoresist composition, a photosensitive glass and a liquid crystal display device. Background Art

[0002] In the field of liquid crystal display, black matrix is ​​usually used to suppress color mixing between red, green and blue monochromatic lights, and to prevent light leakage and improve contrast. Therefore, it is necessary to improve the light-shielding property of the material. Although the chromium metal vapor deposition film method has high light-shielding property, its formation process is complicated and costly. At present, the pigment method is mainly used to achieve the above purpose, that is, the black matrix is ​​prepared with a black pigment liquid containing black pigment.

[0003] Black pigment is generally carbon black. In order to improve the light-shielding property, the concentration of black pigment needs to be increased. However, the higher the concentration of black pigment, the lower the developability, adhesion and stability of the black pigment liquid. In addition, the black pigment liquid also has the problems of low thermal stability and low impedance value. While improving the light-shielding performance of the black pigment liquid, improving its thermal stability and impedance value is also an urgent problem to be solved.

[0004] Therefore, it is urgent to provide a new black pigment to solve the above problems. Summary of the invention

[0005] The purpose of the present application is to provide a black pigment liquid and a preparation method thereof, a photoresist composition, a photosensitive glass and a liquid crystal display device to solve the above problems.

[0006] To achieve the above objectives, this application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a black pigment liquid, the raw materials of which include modified carbon black;

[0008] The modified carbon black comprises carbon black and a coating layer coating the carbon black;

[0009] The coating includes a dopamine polymer.

[0010] Optionally, the black pigment liquid satisfies at least one of the following conditions:

[0011] A. The primary particle size of the carbon black is 20nm-60nm;

[0012] B. the carbon black comprises acidic carbon black and / or neutral carbon black;

[0013] C. The thickness of the coating layer is 0.1nm-500nm;

[0014] D. The raw materials of the black pigment liquid include, by weight:

[0015] The modified carbon black comprises 30 parts to 210 parts, the dispersant comprises 15 parts to 200 parts, the first alkali-soluble resin comprises 15 parts to 200 parts, and the first organic solvent comprises 50 parts to 250 parts.

[0016] Optionally, the black pigment liquid satisfies at least one of the following conditions:

[0017] A. the first alkali-soluble resin comprises an alkali-soluble Cardo resin and / or an acrylic copolymer resin;

[0018] B. the first organic solvent comprises one or more of an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an alcohol solvent, and a nitrogen-containing organic solvent;

[0019] C. the pH value of the carbon black is 2-4;

[0020] D. The thickness of the coating layer is 10nm-200nm.

[0021] The second aspect of the present application provides a method for preparing the black pigment liquid, comprising:

[0022] Mixing raw materials including modified carbon black to prepare the black pigment liquid;

[0023] Wherein, the preparation method of the modified carbon black comprises:

[0024] In a light-proof environment, carbon black, an alkaline compound, dopamine hydrochloride and water are mixed to react and prepare modified carbon black.

[0025] Optionally, the method for preparing the black pigment liquid satisfies at least one of the following conditions:

[0026] A. The reaction time is 5h-20h, and the temperature is 10℃-50℃;

[0027] B. the alkaline compound comprises an alcohol compound and / or aqueous ammonia;

[0028] C. the mass ratio of the dopamine hydrochloride to the carbon black is 5-100:165;

[0029] D. The pH of the mixture for carrying out the reaction is 7<pH≤14.

[0030] The third aspect of the present application provides a photoresist composition, wherein the raw materials thereof, calculated by mass as 100%, include:

[0031] The black pigment liquid comprises 10%-70%, alkali-soluble resin 5%-45%, photopolymerization initiator 0.2%-5%, monomer 2%-50%, and second organic solvent 10%-50%.

[0032] Optionally, the photoresist composition satisfies at least one of the following conditions:

[0033] A. the alkali-soluble resin comprises an alkali-soluble Cardo resin and / or an acrylic copolymer resin;

[0034] B. The photopolymerization initiator includes 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetoxime), benzophenone, 4,4'-di(N,N-diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylbenzophenone, thioxanthone, 2 - one or more of chlorothioxanthone, 1-hydroxycyclohexylbenzophenone, tert-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoquininone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone and 2-methyl-1[4-(methylthio)phenyl]-2-morpholinylpropane-1-one;

[0035] C. the monomer comprises an acrylic acid compound containing 3 or more ethylenically unsaturated groups and / or a methacrylate compound containing 3 or more ethylenically unsaturated groups;

[0036] D. The second organic solvent includes one or more of ether organic solvents, ether ester organic solvents, ketone organic solvents, alcohol solvents, and nitrogen-containing organic solvents.

[0037] Optionally, the photoresist composition satisfies at least one of the following conditions:

[0038] A. The acrylic acid containing more than three ethylenically unsaturated groups includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate;

[0039] B. The methacrylate compound containing more than three ethylenically unsaturated groups includes one or more of trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, and sorbitol tetramethacrylate.

[0040] The fourth aspect of the present application provides a photosensitive glass, comprising the photoresist composition.

[0041] A fifth aspect of the present application provides a liquid crystal display device, comprising the photosensitive glass.

[0042] Compared with the prior art, the beneficial effects of this application include:

[0043] The black pigment liquid provided in the present application has a dopamine polymer with extremely strong light absorption performance, high impedance and excellent storage stability. Dopamine polymer coating can increase the affinity of carbon black with organic solvents, greatly improve its dispersibility in organic solvents, thereby facilitating the application of carbon black in the liquid phase. Dopamine polymer coating can increase the adhesion of carbon black to other organic and inorganic materials, so it can adhere firmly to most solid surfaces without other additional conditions, which helps to firmly combine carbon black with other materials to form a composite material.

[0044] The preparation method of the black pigment liquid provided in the present application is to oxidize dopamine hydrochloride in an alkaline environment to form a dopamine polymer with strong adhesion performance and can firmly adhere to the carbon black surface without other additional conditions. The method is simple to operate and the raw materials are easily available.

[0045] The photoresist composition provided in the present application has high impedance and high OD performance.

[0046] The photosensitive glass and liquid crystal display device provided by the present application have good light-shielding performance and long service life. DETAILED DESCRIPTION

[0047] As used herein:

[0048] "Prepared from" is synonymous with "comprising." As used herein, the terms "comprising," "including," "having," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises the listed elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.

[0049] The conjunction "consisting of excludes any unspecified element, step, or component. If used in a claim, this phrase renders the claim closed-ended so that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause of the body of a claim rather than immediately following the subject matter, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0050] When an amount, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pairing of any range upper limit or preferred value with any range lower limit or preferred value, regardless of whether the range is disclosed separately. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted as including ranges "1 to 4", "1 to 3", "1 to 2", "1 to 2 and 4 to 5", "1 to 3 and 5", etc. When a numerical range is described in this article, unless otherwise stated, the range is intended to include its end values ​​and all integers and fractions within the range.

[0051] In these examples, parts and percentages are by mass unless otherwise indicated.

[0052] "Parts by mass" refers to the basic unit of measurement for expressing the mass ratio of multiple components. 1 part can represent any unit mass, such as 1g or 2.689g. If we say that the mass of component A is a parts and the mass of component B is b parts, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, indicating a multiple factor). It should not be misunderstood that, unlike the mass parts, the sum of the mass of all components is not limited to 100 parts.

[0053] "And / or" is used to indicate that one or both of the stated situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0054] It should be noted that there are also some limitations and challenges in the effect of polydopamine modification on carbon black. Polydopamine-modified carbon black needs to be controlled, otherwise too much or too little modification will affect the performance of carbon black. Polydopamine-modified carbon black has different stability under different environmental conditions, and the impact of environmental factors on its performance needs to be considered.

[0055] In a first aspect, the present application provides a black pigment liquid, the raw materials of which include modified carbon black;

[0056] The modified carbon black comprises carbon black and a coating layer coating the carbon black;

[0057] The coating includes a dopamine polymer.

[0058] In some embodiments, the black pigment liquid satisfies at least one of the following conditions:

[0059] A. The primary particle size of the carbon black is 20nm-60nm;

[0060] Optionally, the primary particle size of the carbon black may be 20 nm, 30 nm, 40 nm, 50 nm, 60 nm or any value between 20 nm and 60 nm;

[0061] It should be noted that when the primary particle size of carbon black is less than 20 nm or greater than 60 nm, it does not have sufficient light-shielding properties and has poor storage stability;

[0062] B. the carbon black comprises acidic carbon black and / or neutral carbon black;

[0063] C. The thickness of the coating layer is 0.1nm-500nm;

[0064] Optionally, the thickness of the coating layer may be 0.1 nm, 1 nm, 10 nm, 500 nm, or any value between 0.1 nm and 500 nm;

[0065] D. The raw materials of the black pigment liquid include, by weight:

[0066] The modified carbon black comprises 30 parts to 210 parts, the dispersant comprises 15 parts to 200 parts, the first alkali-soluble resin comprises 15 parts to 200 parts, and the first organic solvent comprises 50 parts to 250 parts.

[0067] Optionally, the raw materials of the black pigment liquid are measured by weight: the modified carbon black can be 30 parts, 60 parts, 120 parts, 180 parts, 210 parts or any value between 30 parts and 210 parts; the dispersant can be 15 parts, 50 parts, 100 parts, 150 parts, 200 parts or any value between 15 parts and 200 parts; the first alkali-soluble resin can be 15 parts, 50 parts, 100 parts, 150 parts, 200 parts or any value between 15 parts and 200 parts; and the first organic solvent can be 50 parts, 100 parts, 150 parts, 200 parts, 250 parts or any value between 50 parts and 250 parts.

[0068] Preferably, the raw materials of the black pigment liquid include, by weight:

[0069] The modified carbon black comprises 60 parts to 180 parts, the dispersant comprises 30 parts to 90 parts, the first alkali-soluble resin comprises 30 parts to 90 parts, and the first organic solvent comprises 50 parts to 250 parts.

[0070] In some embodiments, the black pigment liquid satisfies at least one of the following conditions:

[0071] A. the first alkali-soluble resin comprises an alkali-soluble Cardo resin and / or an acrylic copolymer resin;

[0072] It should be noted that the first alkali-soluble resin refers to a resin having an alkali-soluble group such as a carboxyl group, a hydroxyl group, or an acid anhydride;

[0073] It should also be noted that the first alkali-soluble resin can improve the developability and pattern forming properties, and in addition, the alkali-soluble resin can also be used as a dispersant and a binder;

[0074] B. the first organic solvent comprises one or more of an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an alcohol solvent, and a nitrogen-containing organic solvent;

[0075] It should be noted that the boiling point of the first organic solvent is 100°C-200°C;

[0076] Preferably, the first organic solvent comprises propylene glycol monomethyl ether acetate;

[0077] C. the pH value of the carbon black is 2-4;

[0078] Optionally, the pH value of carbon black can be 2, 3, 4 or any value between 2 and 4;

[0079] It should be noted that when the pH value of carbon black is 2-4, its oxidation degree will be lower than that of conventional basic carbon black.

[0080] D. The thickness of the coating layer is 10nm-200nm.

[0081] Optionally, the thickness of the coating layer may be 10 nm, 100 nm, 200 nm or any value between 10 nm and 200 nm.

[0082] It should be noted that when the coating layer has a thickness of 10nm-200nm, the light shielding performance of the black matrix can be effectively improved, and the modified carbon black has extremely strong thermal stability and low conductivity. However, when the thickness is less than 10nm or greater than 200nm, the above performance improvement or performance enhancement is not obvious.

[0083] The second aspect of the present application provides a method for preparing the black pigment liquid, comprising:

[0084] Mixing raw materials including modified carbon black to prepare the black pigment liquid;

[0085] Wherein, the preparation method of the modified carbon black comprises:

[0086] In a light-proof environment, carbon black, an alkaline compound, dopamine hydrochloride and water are mixed to react and prepare modified carbon black.

[0087] In some embodiments, the method for preparing the black pigment liquid satisfies at least one of the following conditions:

[0088] A. The reaction time is 5h-20h, and the temperature is 10℃-50℃;

[0089] Optionally, the reaction time can be 5 h, 10 h, 15 h, 20 h or any value between 5 h and 20 h, and the temperature can be 10 ° C, 20 ° C, 30 ° C, 40 ° C, 50 ° C or any value between 10 ° C and 50 ° C;

[0090] Preferably, the reaction time is 5h-15h, and the temperature is 15°C-40°C;

[0091] B. the alkaline compound comprises an alcohol compound and / or aqueous ammonia;

[0092] Preferably, the alkaline compound includes an alcohol compound and ammonia water. The alcohol compound not only serves as a dispersant for the solution, but also removes impurities on the surface of carbon black to improve the quality of carbon black, which is more conducive to the adsorption of dopamine polymer. At the same time, the ratio of dopamine hydrochloride is matched to ensure sufficient adsorption of dopamine polymer.

[0093] In some embodiments, the concentration of aqueous ammonia is 10 wt%-35 wt%, preferably 15 wt%-30 wt%;

[0094] C. the mass ratio of the dopamine hydrochloride to the carbon black is 5-100:165;

[0095] Optionally, the mass ratio of dopamine hydrochloride to carbon black can be 5:165, 10:165, 50:165, 100:165 or any value between 5-100:165;

[0096] It should be noted that the mass ratio of dopamine hydrochloride to carbon black is in the range of 5-100:165. The more tightly and fully the dopamine polymer obtained after the reaction is wrapped, the more wasteful it will be.

[0097] D. The pH of the mixture for carrying out the reaction is 7<pH≤14.

[0098] Optionally, the pH of the reaction mixture may be 7.5, 8, 10, 12, 14, or any value greater than 7 and less than or equal to 14.

[0099] It should be noted that while the alkaline compound removes impurities on the surface of carbon black, it also makes the system alkaline, allowing dopamine hydrochloride to oxidize and better adhere to the surface of carbon black.

[0100] In some embodiments, the black pigment liquid is prepared for the purpose of removing impurities and reducing defects, etc., and is filtered through a filter. As a filter, any filter that has been used for filtering purposes in the past can be used without particular limitation; examples include filters using raw materials such as fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (such as nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density, ultra-high molecular weight polyolefin resins). Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

[0101] The pore size of the filter is preferably about 0.01μm-7.0μm, preferably about 0.01μm-3.0μm, and more preferably about 0.05μm-0.5μm; by setting it to this range, in the later process, fine impurities that hinder the preparation of a uniform and smooth photoresist composition can be reliably removed; and it is also preferred to use fibrous filter materials, and examples of filter materials include polypropylene fibers, nylon fibers, glass fibers, etc.

[0102] When using filters, different filters may be combined, and filtering in the filters may be performed only once or twice or more.

[0103] Furthermore, within the above range, filters with different pore sizes may be combined, and the pore size may refer to the nominal value of the filter manufacturer.

[0104] When performing filtration multiple times, a filter formed of the same material as the previous filter can be used.

[0105] The third aspect of the present application provides a photoresist composition, wherein the raw materials thereof, calculated by mass as 100%, include:

[0106] The black pigment liquid comprises 10%-70%, alkali-soluble resin 5%-45%, photopolymerization initiator 0.2%-5%, monomer 2%-50%, and second organic solvent 10%-50%.

[0107] Optionally, the raw materials of the photoresist composition are 100% by mass, the black pigment liquid can be 10%, 20%, 30%, 40%, 50%, 60%, 70% or any value between 10% and 70%, the alkali-soluble resin can be 5%, 15%, 25%, 35%, 45% or any value between 5% and 45%, the photopolymerization initiator can be 0.2%, 1%, 2%, 3%, 4%, 5% or any value between 0.2% and 5%, the monomer can be 2%, 5%, 10%, 20%, 30%, 40%, 50% or any value between 2% and 50%, and the second organic solvent can be 10%, 20%, 30%, 40%, 50% or any value between 10% and 50%.

[0108] Preferably, the raw materials of the photoresist composition, calculated by mass as 100%, include:

[0109] The black pigment liquid comprises 20%-60%, alkali-soluble resin 7%-45%, photopolymerization initiator 0.2%-5%, monomer 2%-20%, and second organic solvent 25%-35%.

[0110] In some embodiments, the photoresist composition satisfies at least one of the following conditions:

[0111] A. the alkali-soluble resin comprises an alkali-soluble Cardo resin and / or an acrylic copolymer resin;

[0112] It should be noted that the second alkali-soluble resin refers to a resin having an alkali-soluble group such as a carboxyl group, a hydroxyl group, or an acid anhydride;

[0113] It should also be noted that the second alkali-soluble resin can improve the developability and pattern forming properties. In the development process, it is more soluble than the developer (especially the alkali developer) used. In addition, the alkali-soluble resin can also be used as a dispersant and a binder.

[0114] B. The photopolymerization initiator includes 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetoxime), benzophenone, 4,4'-di(N,N-diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylbenzophenone, thioxanthone, 2 - one or more of chlorothioxanthone, 1-hydroxycyclohexylbenzophenone, tert-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoquininone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone and 2-methyl-1[4-(methylthio)phenyl]-2-morpholinylpropane-1-one;

[0115] It should be noted that the photopolymerization initiator can generate free radical active species by bond cleavage and / or reaction through exposure, and the free radical active species can be used to photocure the compound having two or more free radical polymerizable groups to form a pattern, wherein the cationic photopolymerization initiator can be decomposed into cations or proton acids under the action of light, thereby initiating a cationic polymerization reaction to form a pattern;

[0116] C. the monomer comprises an acrylic acid compound containing 3 or more ethylenically unsaturated groups and / or a methacrylate compound containing 3 or more ethylenically unsaturated groups;

[0117] It should be noted that the cured product of the polymerization of the monomers is finally filled in the film of the pixel as the acrylic resin component contained in the alkali-soluble resin;

[0118] D. The second organic solvent includes one or more of ether organic solvents, ether ester organic solvents, ketone organic solvents, alcohol solvents, and nitrogen-containing organic solvents.

[0119] It should be noted that the boiling point of the second organic solvent is 100°C-200°C.

[0120] Preferably, the second organic solvent comprises propylene glycol monomethyl ether acetate.

[0121] In some embodiments, the ether organic solvent includes one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether.

[0122] In some embodiments, the ether ester organic solvent includes one or more of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate.

[0123] In some embodiments, the ketone organic solvent includes one or more of methyl isobutyl ketone, cyclohexanone, 2-heptanone, and delta-butyrolactone.

[0124] In some embodiments, the alcohol solvent includes ester organic solvents such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, 3-methyl-3-methoxybutyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, and n-pentyl formate; or one or more of methanol, ethanol, isopropanol, and butanol.

[0125] In some embodiments, the nitrogen-containing organic solvent includes one or more of N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0126] In some embodiments, the photoresist composition satisfies at least one of the following conditions:

[0127] A. The acrylic acid containing more than three ethylenically unsaturated groups includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate;

[0128] B. The methacrylate compound containing more than three ethylenically unsaturated groups includes one or more of trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, and sorbitol tetramethacrylate.

[0129] The fourth aspect of the present application provides a photosensitive glass, comprising the photoresist composition.

[0130] A fifth aspect of the present application provides a liquid crystal display device, comprising the photosensitive glass.

[0131] The embodiments of the present application will be described in detail below in conjunction with specific examples, but it will be appreciated by those skilled in the art that the following examples are only used to illustrate the present application and should not be considered as limiting the scope of the present application. If specific conditions are not specified in the examples, they are carried out according to normal conditions or the conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0132] Example 1

[0133] This embodiment provides a black pigment liquid (the black pigment liquid provided in this embodiment is named black pigment liquid-1) and a preparation method thereof, wherein the preparation method of modified carbon black comprises:

[0134] 165 g of carbon black Raven 1080 (pH 3, average particle size 28 nm) was mixed with 450 g of water to prepare a slurry, to which 200 g of ethanol and 10 g of 25% ammonia water were added, and heated and stirred to prepare a uniform suspension of carbon black with a content of 5%;

[0135] 18 g of dopamine hydrochloride was added to the uniform suspension of carbon black. After complete dissolution, the pH value of the obtained mixture was 10. The mixture was stirred at 30°C in the dark to carry out an oxidative polymerization reaction. After 10 hours, the obtained product was centrifuged at high speed and washed three times with deionized water to obtain modified carbon black coated with dopamine polymer. The thickness of the dopamine polymer coating layer was 1 μm.

[0136] The preparation method of black pigment liquid comprises:

[0137] 100 g of modified carbon black, 60 g of dispersant BYK-161, 50 g of alkali-soluble resin RD-SV-200 (solid content 40%) and 190 g of solvent propylene glycol monomethyl ether acetate were put into a bead mill and dispersed for 12 hours to prepare black pigment liquid-1.

[0138] This embodiment also provides a photoresist composition and a preparation method thereof, comprising:

[0139] The raw materials are 100% by mass, and 50% of the above black pigment liquid-1, 12.5% ​​of alkali-soluble resin RD-SV-200, 1% of photopolymerization initiator OXE 01, 5% of monomer DPHA, and 31.5% of organic solvent propylene glycol methyl ether acetate are mixed to prepare a photoresist composition.

[0140] Example 2

[0141] The black pigment liquid provided in this embodiment is named black pigment liquid-2, and the difference from Example 1 is that 9 g of dopamine hydrochloride is used in the preparation process of modified carbon black.

[0142] This embodiment also provides a photoresist composition, which is consistent with the method of Example 1, and the raw materials include the black pigment liquid-2 prepared in this embodiment.

[0143] Example 3

[0144] The black pigment liquid provided in this embodiment is named black pigment liquid-3, and the difference from Example 1 is that 27 g of dopamine hydrochloride is used in the preparation process of modified carbon black.

[0145] This embodiment also provides a photoresist composition, which is consistent with the method of Example 1, and the raw materials include the black pigment liquid-3 prepared in this embodiment.

[0146] Example 4

[0147] The black pigment liquid provided in this embodiment is named black pigment liquid-4, and the difference from Example 1 is that 36 g of dopamine hydrochloride is used in the preparation process of modified carbon black.

[0148] This embodiment also provides a photoresist composition, which is consistent with the method of Example 1, and the raw materials include the black pigment liquid-4 prepared in this embodiment.

[0149] Comparative Example 1

[0150] The black pigment liquid provided in this comparative example is named black pigment liquid-5, and the difference from Example 1 is that during the preparation of the modified carbon black, the modified carbon black in the black pigment liquid is replaced by its raw material carbon black Raven 1080.

[0151] This comparative example also provides a photoresist composition, which is consistent with the method of Example 1, and the raw materials include the black pigment liquid-5 prepared in this comparative example.

[0152] Comparative Example 2

[0153] The black pigment liquid provided in this comparative example is named black pigment liquid-6, and the difference from Example 1 is that during the preparation of the modified carbon black, dopamine hydrochloride is replaced with EHPE-3150, manufactured by Daicel Japan.

[0154] This comparative example also provides a photoresist composition, which is consistent with the method of Example 1, and the raw materials include the black pigment liquid-6 prepared in this comparative example.

[0155] Comparative Example 3

[0156] The black pigment liquid provided in this comparative example is named black pigment liquid-7, and the difference from Example 1 is that during the preparation of the modified carbon black, the modified carbon black in the black pigment liquid is replaced by its raw material carbon black Raven 1080 and dopamine hydrochloride, wherein the mass ratio of carbon black Raven 1080 to dopamine hydrochloride is 165:18.

[0157] This comparative example also provides a photoresist composition, which is consistent with the method of Example 1, and the raw materials include the black pigment liquid-7 prepared in this comparative example.

[0158] The data on the types of raw materials and their mass amounts of the photoresist compositions provided in the above examples and comparative examples are shown in Table 1.

[0159] Table 1 Raw material data of photoresist composition

[0160]

[0161]

[0162] The black pigment liquids prepared in the above-mentioned embodiments and comparative examples were respectively subjected to viscosity stability tests. The test method is as follows: after testing the initial viscosity of the black pigment liquid, the black pigment liquid is placed in a 45°C oven and stored for 2 weeks to test the viscosity stability and calculate the difference between the viscosity and the initial viscosity. The specific test results are shown in Table 2.

[0163] Table 2 Viscosity stability test

[0164] Black pigment liquid Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Viscosity stability 0.2 0.3 0.16 0.15 0.56 0.39 0.40

[0165] The photoresist combinations prepared in the above-mentioned embodiments and comparative examples were subjected to performance tests, including surface resistance and OD value tests. The specific test results are shown in Table 3.

[0166] The surface resistance test method is as follows: the photoresist composition (in an amount to achieve a film thickness of 1.0 μm after baking) is coated on a 100 mm × 100 mm glass using a spin coater, pre-baked at 90°C for 1 minute, and then, the surface resistance is measured using a luminous intensity of 30 mW / cm 2 Ultra-high pressure mercury lamp with i-ray, irradiating 80mJ / cm without mask 2 The ultraviolet rays were used for photocuring reaction, and then the surface resistance was measured using a hot air dryer at the test conditions of 230℃ / 30min and 250℃ / 2h.

[0167] The OD value was tested by using a spin coater to coat the photoresist composition (in an amount to achieve a film thickness of 1.0 μm after baking) on ​​a 100 mm × 100 mm glass, pre-baking at 90 ° C for 1 minute, and then using a luminous intensity of 30 mW / cm 2 Ultra-high pressure mercury lamp with i-ray, irradiation without mask 80mJ / cm 2 The ultraviolet light is used to carry out the photocuring reaction and the OD value is measured.

[0168] Table 3 Performance test

[0169]

[0170] analyze:

[0171] As shown in Table 2, the viscosity of the black pigment liquid prepared by Examples 1-4 was basically unchanged after the viscosity stability test; the black pigment liquid prepared by Comparative Examples 1-2 had poor viscosity stability, and it was speculated that the carbon black did not wrap the dopamine polymer and had poor dispersibility; the black pigment liquid prepared by Comparative Example 3 had poor stability, indicating that the carbon black did not wrap the dopamine polymer modification step, and the dopamine hydrochloride was directly mixed and added, and good wrapping modification was not achieved, resulting in poor stability;

[0172] It can be seen from Table 3 that the impedance values ​​of the photoresist compositions prepared by Examples 1-4 are substantially unchanged after heat treatment; the impedance values ​​of the photoresist compositions prepared by Comparative Examples 1-3 are greatly changed after heat treatment, and have poor thermal stability.

[0173] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

[0174] In addition, those skilled in the art will appreciate that, although some embodiments herein include certain features included in other embodiments but not other features, the combination of features of different embodiments is meant to be within the scope of the present application and form different embodiments. For example, in the above claims, any one of the claimed embodiments may be used in any combination. The information disclosed in this background technology section is intended only to deepen the understanding of the overall background technology of the present application and should not be regarded as an admission or in any form of implication that the information constitutes prior art known to those skilled in the art.

Claims

1. A black pigment liquid, characterized in that: Its raw materials include modified carbon black; The modified carbon black comprises carbon black and a coating layer coating the carbon black; The coating includes a dopamine polymer.

2. The black pigment liquid according to claim 1, characterized in that: At least one of the following conditions is met: A. The primary particle size of the carbon black is 20nm-60nm; B. the carbon black comprises acidic carbon black and / or neutral carbon black; C. The thickness of the coating layer is 0.1nm-500nm; D. The raw materials of the black pigment liquid include, by weight: The modified carbon black comprises 30 parts to 210 parts, the dispersant comprises 15 parts to 200 parts, the first alkali-soluble resin comprises 15 parts to 200 parts, and the first organic solvent comprises 50 parts to 250 parts.

3. The black pigment liquid according to claim 2, characterized in that: At least one of the following conditions is met: A. the first alkali-soluble resin comprises an alkali-soluble Cardo resin and / or an acrylic copolymer resin; B. the first organic solvent comprises one or more of an ether organic solvent, an ether ester organic solvent, a ketone organic solvent, an alcohol solvent, and a nitrogen-containing organic solvent; C. the pH value of the carbon black is 2-4; D. The thickness of the coating layer is 10nm-200nm.

4. A method for preparing the black pigment liquid according to any one of claims 1 to 3, characterized in that: include: Mixing raw materials including modified carbon black to prepare the black pigment liquid; Wherein, the preparation method of the modified carbon black comprises: In a light-proof environment, carbon black, an alkaline compound, dopamine hydrochloride and water are mixed to react and prepare modified carbon black.

5. The method for preparing the black pigment liquid according to claim 4, characterized in that: At least one of the following conditions is met: A. The reaction time is 5h-20h, and the temperature is 10℃-50℃; B. the alkaline compound comprises an alcohol compound and / or aqueous ammonia; C. the mass ratio of the dopamine hydrochloride to the carbon black is 5-100:165; D. The pH of the mixture for carrying out the reaction is 7<pH≤14.

6. A photoresist composition, characterized in that: The raw materials thereof, calculated by mass as 100%, include: 10%-70% of the black pigment liquid as described in any one of claims 1 to 3, 5%-45% of an alkali-soluble resin, 0.2%-5% of a photopolymerization initiator, 2%-50% of a monomer, and 10%-50% of a second organic solvent.

7. The photoresist composition according to claim 6, characterized in that At least one of the following conditions is met: A. the alkali-soluble resin comprises an alkali-soluble Cardo resin and / or an acrylic copolymer resin; B. The photopolymerization initiator includes 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetoxime), benzophenone, 4,4'-di(N,N-diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α - one or more of hydroxyisobutylbenzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylbenzophenone, tert-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzoquininone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone; C. the monomer comprises an acrylic acid compound containing 3 or more ethylenically unsaturated groups and / or a methacrylate compound containing 3 or more ethylenically unsaturated groups; D. The second organic solvent includes one or more of ether organic solvents, ether ester organic solvents, ketone organic solvents, alcohol solvents, and nitrogen-containing organic solvents.

8. The photoresist composition according to claim 7, characterized in that At least one of the following conditions is met: A. The acrylic acid containing more than three ethylenically unsaturated groups includes one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; B. The methacrylate compound containing more than three ethylenically unsaturated groups includes one or more of trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, and sorbitol tetramethacrylate.

9. A photosensitive glass, characterized in that: The photoresist composition comprises the photoresist composition according to claim 7 or 8.

10. A liquid crystal display device, characterized in that: Including the photosensitive glass as described in claim 9.

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