Pigment dispersant, pigment dispersion liquid and photoresist composition

Abstract

The invention provides a pigment dispersant, a pigment dispersion liquid and a photoresist composition, and relates to the field of pigment dispersants. The pigment dispersing agent comprises at least one first repeating unit shown in a formula I, at least one second repeating unit shown in a formula II and at least one third repeating unit; the pigment dispersing agent comprises a second repeating unit with a blocked isocyanate group, an end-capping reagent in the blocked isocyanate group is used for protecting an isocyanate group with high reactivity, the blocked isocyanate group can be dissociated due to heating to regenerate the isocyanate group, and the isocyanate group and reactive functional groups contained in other components can react with each other to regenerate the reactive functional groups. Such as acid groups, hydroxyl groups, amino groups and the like, thereby forming a cured product with high cross-linking density. The dispersion liquid prepared by using the dispersing agent can further improve the curing degree in a baking stage, reduces the generation of chromatic aberration, and can obviously improve the heat resistance of the pigment, thereby obtaining high transmittance.

Description

Technical Field

[0001] The present application relates to the field of pigment dispersants, and particularly to a pigment dispersant, a pigment dispersion liquid, and a photoresist composition. Background Art

[0002] Polyhalogenated metal phthalocyanine pigments, such as C.I. Pigment Green 36 and C.I. Pigment Green 58, exhibit a finer particle structure compared to the pigments used in traditional inks or coatings. This characteristic should theoretically be beneficial for improving the color saturation and clarity of color filters because finer pigment particles can be more effectively dispersed in the medium, reducing scattering and thus increasing the light transmission efficiency. However, in practical applications, this advantage faces challenges.

[0003] Due to the high degree of micronization of polyhalogenated metal phthalocyanine pigments, their sensitivity increases significantly. When these pigments are dispersed into a dispersion liquid and applied to a photosensitive composition, they are prone to yellow edge during the baking stage, resulting in a decrease in heat resistance and a reduction in transmittance. This not only affects the color performance of the color filter but may also have an adverse impact on the visual effect and energy efficiency of the entire display device.

[0004] Therefore, how to effectively improve the dispersibility of polyhalogenated metal phthalocyanine pigments while maintaining their fine particle advantage has become an urgent problem to be solved in the current color filter manufacturing technology. Summary of the Invention

[0005] The purpose of the present application is to provide a pigment dispersant, a pigment dispersion liquid, and a photoresist composition to solve the above problems.

[0006] To achieve the above purpose, the present application adopts the following technical solutions:

[0007] A pigment dispersant includes at least one first repeating unit represented by Formula I, at least one second repeating unit represented by Formula II, and at least one third repeating unit;

[0008] The third repeating unit includes at least one of the structures represented by Formula III and Formula IV;

[0009]

[0010] wherein, R 1 、R 3 、R 6 are the same or different and are independently selected from H or C 1-10 alkyl;

[0011] R 2 is selected from C 1-10 alkyl, C 1-10 alkyl-aryl;

[0012] R 4 selected from C 1-10 alkyl;

[0013] R 5 selected from unsubstituted or C-substituted heterocyclic groups which are substituted by one or more C 1-10 alkyl, unsubstituted or C-substituted heteroaryl groups which are substituted by one or more C 1-10 alkyl, unsubstituted or C-substituted cycloalkyl groups which are substituted by one or more C 1-10 alkyl, unsubstituted or C-substituted aryl groups which are substituted by one or more C 1-10 alkyl;

[0014] Each R 7 、R 8 、R 9 is the same or different and is independently selected from C 1-10 alkyl;

[0015] R 10 selected from C 1-10 alkyl-aryl.

[0016] According to an embodiment of the present application, the first repeating unit includes at least one of the following structures:

[0017]

[0018] According to an embodiment of the present application, the second repeating unit includes the following structure:

[0019]

[0020] According to an embodiment of the present application, the third repeating unit includes at least one of the following structures:

[0021]

[0022] According to an embodiment of the present application, the second repeating unit is located between the first repeating unit and the third repeating unit.

[0023] According to an embodiment of the present application, the weight-average molecular weight of the dispersant is 7,000 to 8,000.

[0024] According to an embodiment of the present application, the pigment dispersant includes at least one of the following repeating units:

[0025]

[0026]

[0027] The present application also provides a pigment dispersion liquid, and the pigment dispersion liquid includes the pigment dispersant described above.

[0028] According to an embodiment of the present application, the photoresist composition further comprises a pigment and a first organic solvent;

[0029] Preferably, the pigment comprises an organic pigment having a green color.

[0030] The present application also provides a photoresist composition, which comprises the pigment dispersion liquid described above;

[0031] Preferably, the photoresist composition further comprises an alkali-soluble resin, a photoinitiator, an ethylenically unsaturated compound, and a second organic solvent.

[0032] The alkali-soluble resin is an alkali-soluble resin having an alkali-soluble group, and the alkali-soluble group includes at least one of a carboxyl group, a hydroxyl group, and an acid anhydride;

[0033] The ethylenically unsaturated compound includes an acrylic or methacrylic acid ester compound containing more than 3 ethylenically unsaturated groups.

[0034] Compared with the prior art, the beneficial effects of the present application include:

[0035] The pigment dispersant of the present application includes a second repeating unit having a blocked isocyanate group. The blocking agent in the blocked isocyanate group is used to protect the highly reactive isocyanate group. The blocked isocyanate group dissociates due to heating to regenerate the isocyanate group, and the isocyanate group reacts with reactive functional groups contained in other components, such as acid groups, hydroxyl groups, amino groups, etc., thereby forming a cured product with a high crosslinking density. Therefore, the dispersion liquid prepared using this dispersant can further improve the curing degree during the baking stage, reduce the generation of color difference, significantly improve the heat resistance of the pigment, and thereby obtain a high transmittance. Detailed Embodiments

[0036] As used herein, the terms:

[0037] "Prepared from" is synonymous with "comprising". As used herein, the terms "comprising", "including", "having", "containing", or any other variation thereof are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or device containing the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or device.

[0038] The conjunctive "consisting of" excludes any unrecited element, step, or component. If used in a claim, this phrase will render the claim closed, excluding materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of" appears in a clause within the body of a claim rather than immediately following the subject, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0039] When an equivalent, concentration, or other value or parameter is recited 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 to specifically disclose all ranges formed by any combination of any upper range limit or preferred value with any lower range limit or preferred value, whether or not that range is separately disclosed. For example, when the range "1 - 5" is disclosed, the recited range should be interpreted as including the ranges "1 - 4", "1 - 3", "1 - 2", "1 - 2 and 4 - 5", "1 - 3 and 5", etc. When a numerical range is recited herein, unless otherwise indicated, that range is intended to include its end values and all integers and fractions within that range.

[0040] In these examples, unless otherwise specified, the parts and percentages are by mass.

[0041] "Parts by mass" refers to the basic measurement unit representing the mass ratio relationship of multiple components. 1 part can represent any unit mass, such as 1 g or 2.689 g, etc. If we say that the mass parts of component A is a parts and the mass parts of component B is b parts, it means the mass ratio of component A to component B is a:b. Or, it means the mass of component A is aK and the mass of component B is bK (K is any number representing a multiple factor). It should not be misunderstood that, different from the number of mass parts, the sum of the mass parts of all components is not limited to 100 parts.

[0042] "And / or" is used to indicate that one or both of the stated circumstances may occur. For example, A and / or B includes (A and B) and (A or B).

[0043] To better illustrate the technical solutions provided in this application, before the examples, a general statement of the technical solutions is made as follows:

[0044] A pigment dispersant, comprising at least one first repeating unit represented by formula I, at least one second repeating unit represented by formula II, and at least one third repeating unit;

[0045] The third repeating unit includes at least one of the structures represented by formula III and formula IV;

[0046]

[0047]

[0048] Among them, R 1 and R 3 and R 6 are the same or different and are independently selected from H or C 1-10 alkyl;

[0049] R 2 is selected from C 1-10 alkyl, C 1-10 alkyl-aryl;

[0050] R 4 is selected from C 1-10 alkyl;

[0051] R 5 is selected from unsubstituted or substituted by one or more C 1-10 alkyl-substituted heterocyclic group, unsubstituted or substituted by one or more C 1-10 alkyl-substituted heteroaryl, unsubstituted or substituted by one or more C 1-10 alkyl-substituted cycloalkyl, unsubstituted or substituted by one or more C 1-10 alkyl-substituted aryl;

[0052] Each R 7 and R 8 and R 9 are the same or different and are independently selected from C 1-10 alkyl;

[0053] R 10 is selected from C 1-10 alkyl-aryl.

[0054] It should be noted that C 1-10 alkyl represents a straight-chain or branched-chain saturated monovalent hydrocarbon group having 1 to 10 carbon atoms. C 1-10 alkyl includes but is not limited to methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, 2-ethylhexyl, etc. or their isomers.

[0055] Aryl represents a monocyclic, bicyclic or tricyclic hydrocarbon ring having monovalent aromaticity or partial aromaticity. Aryl includes, but is not limited to, phenyl, biphenyl, indenyl, tetrahydronaphthyl, dihydronaphthyl, naphthyl, fluorenyl, anthracenyl. Heterocyclic group represents a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane, which is a non-aromatic cyclic group containing 1-5 heteroatoms independently selected from N, O and S. Heterocyclic groups include, but are not limited to: azetidinyl, oxetanyl, tetrahydrofuranyl, dioxolanyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrroline, tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl, diazepanyl.

[0056] Heteroaryl represents an aromatic or partially aromatic compound containing 1-5 heteroatoms independently selected from N, O and S. Heteroaryl includes, but is not limited to, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl.

[0057] Cycloalkyl represents a saturated monovalent monocyclic or bicyclic hydrocarbon ring. Cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl.

[0058] According to an embodiment of the present application, the first repeating unit includes at least one of the following structures:

[0059]

[0060] According to an embodiment of the present application, the second repeating unit includes the following structure:

[0061]

[0062] According to an embodiment of the present application, the third repeating unit includes at least one of the following structures:

[0063]

[0064] According to an embodiment of the present application, the second repeating unit is located between the first repeating unit and the third repeating unit.

[0065] According to an embodiment of the present application, the weight average molecular weight of the dispersant is 7000-8000.

[0066] According to an embodiment of the present application, the pigment dispersant includes at least one of the following repeating units:

[0067]

[0068] The present application also provides a pigment dispersion liquid, which includes the pigment dispersant described above.

[0069] According to an embodiment of the present application, the pigment dispersion further includes components such as pigments and a first organic solvent.

[0070] According to an embodiment of the present application, the pigment includes an organic pigment having a green color; among them, the organic pigment having a green color includes C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 60, 61 or 62, preferably C.I. Pigment Green 58, 59.

[0071] The present application does not limit the preparation method of the pigment dispersion. For example: the pigment dispersant can be first added to the first organic solvent, stirred to prepare a dispersant solution, and then the dispersant solution is mixed with other components as required. During this process, a well-known stirrer or disperser can be used for dispersion.

[0072] The disperser used for dispersion treatment can be a roll mill such as a two-roll or three-roll mill, a ball mill such as a ball mill, a vibration ball mill, a paint conditioner, a continuous disk bead mill, a continuous ring bead mill, etc. The present application does not limit the dispersion conditions of the bead mill. For example, the bead diameter used can be 0.03 - 2.00 mm, preferably 0.05 - 1.0 mm. Specifically, preliminary dispersion can be carried out with 1.0 mm zirconia beads with a larger bead diameter, and then main dispersion can be carried out with 0.1 mm zirconia beads with a smaller bead diameter.

[0073] Among them, the organic pigment accounts for 5 - 30% of the content of the entire pigment dispersion, preferably 10 - 30%. Within this range, the viscosity of the dispersion has good stability.

[0074] Among them, the ratio of the pigment dispersant to the pigment content is 30% - 100%. Within this range, excellent storage stability can be obtained, and the transmittance and heat resistance of the dispersion can be effectively improved.

[0075] The present application also provides a photoresist composition, and the photoresist composition includes the pigment dispersion described above.

[0076] According to an embodiment of the present application, the photoresist composition further includes an alkali-soluble resin, a photoinitiator, an ethylenically unsaturated compound, and a second organic solvent.

[0077] The alkali-soluble resin is an alkali-soluble resin having an alkali-soluble group, and the alkali-soluble group includes at least one of a carboxyl group, a hydroxyl group, and an acid anhydride;

[0078] The alkali-soluble resin includes but is not limited to alkali-soluble Cardo resin and acrylic copolymer resin.

[0079] The ethylenically unsaturated compounds include acrylic or methacrylic ester compounds containing more than 3 ethylenically unsaturated groups. Among them, acrylic acids containing more than 3 ethylenically unsaturated groups include, but are not limited to, pentaerythritol triacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate. Methacrylic ester compounds include, but are not limited to, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate.

[0080] According to some embodiments of the present application, the photopolymerization initiator refers to a photopolymerization initiator that can generate free radicals or cations by irradiating active energy rays such as ultraviolet rays and electron beams. Specifically, the photopolymerization initiator includes, but is not limited to, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-one]-1-(O-acetyl oxime), benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylbenzophenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexylbenzophenone, tert-butyl anthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 1,2-benzquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one and other benzophenone initiators, thioxanthone initiators, anthraquinone initiators, triazine initiators, oxime ester initiators. The above photopolymerization initiators can be used alone or in combination of two or more.

[0081] According to the embodiments of the present application, the first organic solvent and the second organic solvent are the same or different and are independently selected from at least one of ether solvents, ether ester solvents, ketone solvents, ester solvents, alcohol solvents, and nitrogen-containing solvents.

[0082] The ether solvents include at least one 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; the ether ester solvents include at least one of ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol methyl ether acetate), and propylene glycol monoethyl ether acetate; the ketone solvents include at least one of methyl isobutyl ketone, cyclohexanone, 2-heptanone, and δ-butyrolactone; the ester solvents include at least one of 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-amyl formate; the alcohol solvents include at least one of methanol, ethanol, isopropanol, and butanol; the nitrogen-containing solvents include at least one of N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0083] According to an embodiment of the present application, the photoresist composition further includes a leveling agent, and the leveling agent includes a fluorosurfactant F-554.

[0084] The embodiments of the present application will be described in detail below in conjunction with specific examples. However, those skilled in the art will understand that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. For those not specified in the examples, they are carried out under conventional conditions or conditions recommended by the manufacturer. Those reagents or instruments not specified by the manufacturer can be obtained as conventional products through commercial purchase.

[0085] I. Preparation of Pigment Dispersant

[0086] Example 1

[0087] Example 1 provides a pigment dispersant, and its preparation method includes:

[0088] In a 500 mL round-bottom four-necked separable flask equipped with a condenser, an addition funnel, a nitrogen inlet tube, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to fully replace the nitrogen. After the reaction flask was cooled to -60°C, 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel, 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), 8 parts by mass of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxyamino]ethyl acrylate, and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise over 60 minutes.

[0089] After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 20 minutes. After the mixture was allowed to react for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction.

[0090] The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, vacuum dried, purified, and diluted with PGMEA to a solution with a solid content of 30% by mass to obtain pigment dispersant A1. The pigment dispersant A1 had an amine value of 95 mgKOH / g and a weight average molecular weight Mw of 7,600.

[0091] The pigment dispersant A1 includes the following repeating unit, wherein the molar ratio of the monomers from left to right in the repeating unit is 13:19:11:7:27:25.

[0092]

[0093] Example 2

[0094] Embodiment 2 provides a pigment dispersant, and its preparation method comprises:

[0095] In a 500 mL round-bottom four-necked separable flask equipped with a condenser, an addition funnel, a nitrogen inlet tube, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to fully replace the nitrogen. After the reaction flask was cooled to -60°C, 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. Using an addition funnel, 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), 8 parts by mass of 2-[(3,5-dimethyl-1-H-pyrazolyl)carboxyamino]ethyl acrylate, and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise over 60 minutes.

[0096] After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 20 minutes. After the mixture was allowed to react for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction.

[0097] The obtained precursor block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying.

[0098] 50 parts by mass of the obtained block copolymer was dissolved in 213 parts by mass of PGMEA. 3.2 parts by mass of benzyl chloride was added thereto and reacted at 90°C for 12 hours to obtain a PGMEA solution of a salt-type pigment dispersant A2 (solid content 30%). The pigment dispersant A2 had an amine value of 70 mgKOH / g and a weight average molecular weight Mw of 7600.

[0099] The pigment dispersant A2 includes the following repeating unit, wherein the molar ratio of the monomers from left to right in the repeating unit is 13:19:11:7:27:25.

[0100]

[0101] Comparative Example 1

[0102] In a 500 mL round-bottom four-necked separable flask equipped with a condenser, an addition funnel, a nitrogen inlet pipe, a mechanical stirrer, and a digital thermometer, 250 parts by mass of THF and 0.6 parts by mass of lithium chloride were added to fully replace the nitrogen. After the reaction flask was cooled to -60°C, 4.9 parts by mass of butyl lithium (15% by mass hexane solution), 1.1 parts by mass of diisopropylamine, and 1.0 parts by mass of methyl isobutyrate were injected using a syringe. 12.8 parts by mass of 2-ethylhexyl methacrylate (EHMA), 13.7 parts by mass of n-butyl methacrylate (BMA), 9.5 parts by mass of benzyl methacrylate (BzMA), and 17.5 parts by mass of methyl methacrylate (MMA) were added dropwise using an addition funnel over 60 minutes.

[0103] After 30 minutes, 26.7 parts by mass of dimethylaminoethyl methacrylate (DMMA) was added dropwise over 20 minutes. After the mixture was allowed to react for 30 minutes, 1.5 parts by mass of methanol was added to stop the reaction.

[0104] The obtained precursor block copolymer THF solution was reprecipitated in hexane, filtered, vacuum dried for purification, and diluted with PGMEA to a solution with a solid content of 30% by mass to obtain pigment dispersant A3. The pigment dispersant A3 had an amine value of 95 mgKOH / g and a weight average molecular weight Mw of 6,500.

[0105] The pigment dispersant A3 includes the following repeating unit, wherein the molar ratio of the monomers from left to right in the repeating unit is 13:19:11:7:27.

[0106]

[0107] 2. Preparation of alkali soluble resin

[0108] Alkali soluble resins are synthesized by the following method:

[0109] 150 parts by mass of PGMEA were added to the polymerization tank, and after the temperature was raised to 100°C under a nitrogen atmosphere, 22 parts by mass of methacrylic acid (MAA), 64 parts by mass of cyclohexyl methacrylate (CHMA), 32 parts by mass of methyl methacrylate (MMA), 9.5 parts by mass of benzyl methacrylate (BzMA) and 2 parts by mass of a chain transfer agent (n-dodecyl mercaptan) were continuously added dropwise over 1.5 hours. Then, the reaction was continued while maintaining 100°C, and 2 hours after the addition of the main chain forming mixture was completed, 0.1 parts by mass of p-methoxyphenol as a polymerization terminator was added to stop the polymerization. An alkali-soluble resin A4 solution (weight average molecular weight (Mw) 9000, acid value 90 mgKOH / g, solid content 40% by mass) was obtained.

[0110] The alkali soluble resin comprises the following repeating units:

[0111]

[0112] III. Preparation of Pigment Dispersion

[0113] Preparation of Pigment Dispersion B1

[0114] In a 500 ml PE bottle, add 120 parts by mass of PGMEA and 80 parts by mass of pigment dispersant A1, and stir. Add 80 parts by mass of C.I. Pigment Green 58 (A110, manufactured by DIC Corporation) and 150 parts by mass of zirconia beads with a particle size of 2.0 mm, and perform 1-hour oscillation with a paint stirrer (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing. Then change to 200 parts of zirconia beads with a particle size of 0.3 mm, and perform 20-hour dispersion with a paint stirrer as formal crushing to obtain pigment dispersion B1.

[0115] Preparation of Pigment Dispersion B2

[0116] In a 500 ml PE bottle, add 120 parts by mass of PGMEA and 80 parts by mass of pigment dispersant A2, and stir. Add 80 parts by mass of C.I. Pigment Green 58 (A110, manufactured by DIC Corporation) and 150 parts by mass of zirconia beads with a particle size of 2.0 mm, and perform 1-hour oscillation with a paint stirrer (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing. Then change to 200 parts of zirconia beads with a particle size of 0.3 mm, and perform 20-hour dispersion with a paint stirrer as formal crushing to obtain pigment dispersion B2.

[0117] Preparation of Pigment Dispersion B3

[0118] In a 500 ml PE bottle, add 120 parts by mass of PGMEA and 80 parts by mass of pigment dispersant A3, and stir. Add 80 parts by mass of C.I. Pigment Green 58 (A110, manufactured by DIC Corporation) and 150 parts by mass of zirconia beads with a particle size of 2.0 mm, and perform 1-hour oscillation with a paint stirrer (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing. Then change to 200 parts of zirconia beads with a particle size of 0.3 mm, and perform 20-hour dispersion with a paint stirrer as formal crushing to obtain pigment dispersion B3.

[0119] Preparation of Pigment Dispersion B4

[0120] In a 500 ml PE bottle, add 120 parts by mass of PGMEA, 57.14 parts by mass of BYK-2001 (solid content 42%), and stir. Add 80 parts by mass of C.I. Pigment Green 58 (A110, manufactured by DIC Corporation) and 150 parts by mass of zirconia beads with a particle size of 2.0 mm, and perform 1 hour of oscillation using a paint stirrer (manufactured by Asada Iron Works Co., Ltd.) as pre-crushing. Then, change to 200 parts of zirconia beads with a particle size of 0.3 mm and perform 20 hours of dispersion using a paint stirrer as formal crushing to obtain Pigment Dispersion B4.

[0121] IV. Preparation of Photoresist Composition

[0122] Application Example 1

[0123] Mix Pigment Dispersion B1, alkali-soluble resin A4, Irgacure OXE02, DPHA, F-554, and PMA to obtain a photoresist composition. The content relationship of each component in Application Example 1 is shown in Table 1.

[0124] Application Example 2

[0125] Mix Pigment Dispersion B2, alkali-soluble resin A4, Irgacure OXE02, DPHA, F-554, and PMA to obtain a photoresist composition. The content relationship of each component in Application Example 2 is shown in Table 1.

[0126] Comparative Application Example 1

[0127] Mix Pigment Dispersion B3, alkali-soluble resin A4, Irgacure OXE02, DPHA, F-554, and PMA to obtain a photoresist composition. The content relationship of each component in Comparative Application Example 1 is shown in Table 1.

[0128] Comparative Application Example 2

[0129] Mix Pigment Dispersion B4, alkali-soluble resin A4, Irgacure OXE02, DPHA, F-554, and PMA to obtain a photoresist composition. The content relationship of each component in Comparative Application Example 2 is shown in Table 1.

[0130] Table 1 Formulation Table of Photoresist Composition

[0131]

[0132] Among them, the content unit of each component in the table is parts by mass. Irgacure OXE02 is an oxime ester type photoinitiator, manufactured by BASF; DPHA is dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.; F-554 is a fluorine-based surfactant, manufactured by DIC Corporation; PMA is propylene glycol methyl ether acetate, acting as a solvent, manufactured by BASF.

[0133] V. Evaluation of Photoresist Composition

[0134] 5.1 Evaluation of Dispersion Stability

[0135] For the photoresist compositions prepared in Application Examples 1-2 and Comparative Application Examples 1-2, the initial viscosity just after preparation and the viscosity after storage at 25 °C for 7 days were measured respectively, and the viscosity change was confirmed.

[0136] The evaluation criteria for storage stability are as follows:

[0137] A: The absolute value of the difference in viscosity before and after storage is within the measurement error range (less than 0.5 cP);

[0138] B: The absolute value of the difference in viscosity before and after storage is 0.5 cP or more and less than 1.0 cP;

[0139] C: The absolute value of the difference in viscosity before and after storage is 1.0 cP or more;

[0140] Herein, this is the value when the pigment is 10% by mass based on the total mass of the photoresist composition including the solvent.

[0141] 5.2 Brightness Evaluation, Heat Resistance Evaluation

[0142] Using a spin coater, the above photoresist compositions were respectively coated on a glass substrate with a thickness of 0.7 mm such that the chromaticity y after post-baking was 0.580. Then, it was heated and dried on a hot plate at 80 °C for 3 minutes. Without using a photomask, it was irradiated with ultraviolet rays of 60 mJ / cm 2 to obtain a green cured film. The obtained film was post-baked in a dust-free oven at 230 °C for 25 minutes, and the brightness and chromaticity (L0, a0, b0) were measured using "Microscopic Spectrophotometer OSP-SP200" manufactured by Olympus Corporation.

[0143] Thereafter, the obtained film was further post-baked in a dust-free oven at 230 °C for 25 minutes, and the chromaticity (L1, a1, b1) of the colored film was measured.

[0144] ΔEab = {(L1 - L0) 2 + (a1 - a0) 2 + (b1 - b0) 2}1 / 2

[0145] When ΔEab is 3 or less, it is rated as A; when ΔEab exceeds 3 and is 5 or less, it is rated as B; when ΔEab exceeds 5, it is rated as C. The smaller the value of ΔEab, the better the heat resistance evaluation.

[0146] The performance test results of the photoresist compositions prepared in Application Examples 1-2 and Comparative Application Examples 1-2 are shown in Table 2.

[0147] Table 2 Performance Test Results of the Photoresist Compositions Prepared in Application Examples 1-2 and Comparative Application Examples 1-2

[0148] Application Example 1 Application Example 2 Comparative Application Example 1 Comparative Application Example 2 Dispersion Stability A A A B Brightness 63.5 63.6 63.0 61.2 ΔEab A A B C

[0149] As can be seen from Table 2, compared with the photoresist compositions prepared in Comparative Application Examples 1-2, the photoresist compositions prepared in Application Examples 1-2 have higher dispersion stability, higher brightness, and higher heat resistance. It shows that compared with Comparative Example 1, the pigment dispersants prepared in Examples 1 and 2 have higher dispersion stability, higher brightness, and higher heat resistance.

[0150] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some or all of the technical features; and 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.

[0151] In addition, those skilled in the art can understand that although some embodiments herein include certain features included in other embodiments rather than other features, the combination of the features of different embodiments means that it is within the scope of the present application and forms different embodiments. For example, in the above claims, any one of the claimed embodiments can be used in any combination. The information disclosed in this background art section is only intended to deepen the understanding of the overall background art of the present application and should not be regarded as an admission or any form of suggestion that this information constitutes prior art known to those skilled in the art.

Claims

1. A pigment dispersant, characterized in that: It comprises at least one first repeating unit represented by formula I, at least one second repeating unit represented by formula II, and at least one third repeating unit; The third repeating unit comprises at least one of the structures shown in formula III and the structures shown in formula IV; Wherein, R1, R3, and R6 are the same or different and are independently selected from H or C 1-10 alkyl; R2 is selected from C 1-10 Alkyl, C 1-10 Alkyl-aryl; R4 is selected from C 1-10 alkyl; R5 is selected from unsubstituted or substituted with one or more C 1-10 Alkyl-substituted heterocyclic group, unsubstituted or substituted with one or more C 1-10 Alkyl-substituted heteroaryl, unsubstituted or substituted with one or more C 1-10 Alkyl-substituted cycloalkyl, unsubstituted or substituted with one or more C 1-10 Alkyl substituted aryl; Each R7, R8, R9 is the same or different and is independently selected from C 1-10 alkyl; R 10 Selected from C 1-10 Alkyl-aryl.

2. The pigment dispersant according to claim 1, characterized in that The first repeating unit comprises at least one of the following structures:

3. The pigment dispersant according to claim 1, characterized in that The second repeating unit comprises the following structure:

4. The pigment dispersant according to claim 1, characterized in that The third repeating unit comprises at least one of the following structures:

5. The pigment dispersant according to claim 1, characterized in that The second repeating unit is located between the first repeating unit and the third repeating unit.

6. The pigment dispersant according to claim 1, characterized in that The weight average molecular weight of the dispersant is 7000-8000.

7. The pigment dispersant according to any one of claims 1 to 6, characterized in that The pigment dispersant comprises at least one of the following repeating units:

8. A pigment dispersion, characterized in that: The pigment dispersion comprises the pigment dispersant according to any one of claims 1 to 7.

9. The pigment dispersion according to claim 8, characterized in that: The pigment dispersion also includes a pigment and a first organic solvent; Preferably, the pigment comprises an organic pigment having a green color.

10. A photoresist composition, characterized in that: The photoresist composition comprises the pigment dispersion according to claim 8 or 9; Preferably, the photoresist composition further comprises an alkali-soluble resin, a photopolymerization initiator, an ethylenically unsaturated compound and a second organic solvent; The alkali-soluble resin is an alkali-soluble resin having an alkali-soluble group, wherein the alkali-soluble group includes at least one of a carboxyl group, a hydroxyl group, and an acid anhydride; The ethylenically unsaturated compound includes an acrylic acid or methacrylic acid ester compound containing three or more ethylenically unsaturated groups.

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