Sulfonyl-containing polymeric dispersant, color paste and application thereof

Abstract

The invention provides a polymeric dispersant, color paste and application thereof. The polymeric dispersant provided by the invention comprises a copolymer of a sulfonic acid group acrylamide monomer and an acrylate monomer and / or a methacrylate monomer. By using the polymeric dispersant provided by the invention, the development size and image definition of the photoresist can be improved.

Description

Technical Field

[0001] The present invention relates to the technical field of liquid crystal display materials, and in particular to a polymer dispersant, a color paste and applications thereof. Background Art

[0002] As an important component of inks including colored photoresists, color paste has a great impact on the stability and quality of inks, especially the exposure, development and developed images of photoresists. Therefore, the uniformity and stability of color paste are critical, and flocculation and precipitation often occur during the dispersion of color paste, which will lead to problems such as small developed size, unclear image and light color after application in photoresists.

[0003] Polymer dispersants (superdispersants) have both "anchor groups" with pigment-friendly ends and "solvated tail chains" with solvent-friendly ends. The "anchor groups" can be adsorbed on the surface of the pigment, while the "solvated tail chains" form stable steric hindrances to prevent flocculation and form a uniform and stable dispersion system. Compared with small molecule dispersants, superdispersants have the characteristics of low sensitivity to environmental factors such as pH, ions, temperature, etc. of the dispersion system, high stability, long storage time, and reduced system viscosity, and have better development space (Liu Shujing et al., "Properties and Research Progress of Superdispersants"). The method of synthesizing superdispersants in the prior art, for example, using acrylic acid, acrylate, and styrene to form a main chain through free radical polymerization, and grafting with polyetheramines of different molecular weights, can obtain a dispersant with performance close to the enterprise standard sample B-190, but this method has problems such as long synthesis steps, large fineness (10μm), and poor dispersion stability (the fineness increases with storage time).

[0004] Therefore, it is still necessary to develop more dispersants with better dispersing properties. Summary of the invention

[0005] In order to solve one of the above technical problems existing in the prior art, the present invention provides an acrylamide compound containing a sulfonic acid group, which has a significant improvement on the developing performance of the photoresist, especially the developing clarity and the developing size.

[0006] The technical solution of the present invention is as follows:

[0007] In a first aspect, the present invention provides a polymer dispersant, which includes a copolymer of a sulfonic acid acrylamide monomer and an acrylate monomer and / or a methacrylate monomer.

[0008] According to some embodiments of the present invention, the sulfonic acid acrylamide monomer has a structure represented by Formula I,

[0009]

[0010] In Formula I, R1 represents a C1-C12 alkylene group, a C4-C12 cycloalkylene group, a C3-C12 heterocycloalkylene group, a C6-C20 arylene group or a C3-C20 heteroarylene group.

[0011] In some embodiments, in Formula I, R1 represents C1-C6 alkylene or C6-C12 arylene. In some preferred embodiments, in Formula I, R1 represents C2-C4 alkylene and phenylene. The C2-C4 alkylene of the present invention includes but is not limited to methylene, ethylene, propylene, isopropylene, butylene, isobutylene and tert-butylene.

[0012] In some embodiments, the sulfonic acid acrylamide monomer includes 2-acrylamido-2-methyl-1-propane sulfonic acid and / or 2-acrylamidoethane sulfonic acid.

[0013] In some embodiments, the acrylic acid ester monomer has a structure represented by Formula II-1 or Formula II-2, and the methacrylic acid ester monomer has a structure represented by Formula II-3 or Formula II-4:

[0014]

[0015] Wherein, each R2 independently represents a C1-C12 alkyl group, a C4-C12 cycloalkyl group, a C3-C12 heterocycloalkyl group, a C6-C20 aryl group or a C3-C20 heteroaryl group, preferably a C4-C12 alkyl group, a C4-C12 cycloalkyl group or a C6-C12 aryl group; each R3 independently represents a C1-C12 alkylene group, a C4-C12 cycloalkylene group, a C3-C12 heterocycloalkylene group, a C6-C20 arylene group or a C3-C20 heteroarylene group, preferably a C4-C12 alkylene group, a C4-C12 cycloalkylene group or a C6-C12 arylene group; each R4 and each R5 independently represent a C1-C12 alkyl group, preferably a C1-C6 alkyl group, and more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert-butyl group.

[0016] According to some embodiments of the present invention, the acrylic ester monomer includes an ester formed by acrylic acid and one or more selected from C1-C12, preferably C4-C12, fatty alcohols, C1-C12, preferably C4-C12, alicyclic alcohols, and C6-C12 aromatic alcohols.

[0017] According to some embodiments of the present invention, the methacrylate monomer includes an ester formed by methacrylic acid and one or more selected from C1-C12, preferably C4-C12, fatty alcohols, C1-C12, preferably C4-C12, alicyclic alcohols, and C6-C12 aromatic alcohols.

[0018] In some embodiments, the methacrylate monomer and the acrylate monomer further contain a dialkylamine functional group.

[0019] In some embodiments, the acrylic acid ester monomer includes an ester formed by acrylic acid and one or more of isobornyl alcohol, benzyl alcohol, isooctyl alcohol, n-butanol, dimethylaminoethanol, and 2-ethylhexanol. In some preferred embodiments, the acrylic acid ester monomer includes one or more of isobornyl acrylate, benzyl acrylate, isooctyl acrylate, butyl acrylate, dimethylaminoethyl acrylate, and 2-ethylhexyl acrylate.

[0020] In some embodiments, the methacrylate monomer includes an ester formed by methacrylic acid and one or more of isobornyl alcohol, benzyl alcohol, isooctyl alcohol, n-butanol, dimethylaminoethanol, and 2-ethylhexanol. In some preferred embodiments, the methacrylate monomer includes one or more of isobornyl methacrylate, benzyl methacrylate, isooctyl methacrylate, butyl methacrylate, dimethylaminoethyl methacrylate, and 2-ethylhexyl methacrylate.

[0021] According to some embodiments of the present invention, the preparation of the copolymer comprises the following steps:

[0022] The sulfonic acrylamide monomer and the acrylate monomer and / or methacrylate monomer are polymerized in solvent a.

[0023] In some embodiments, the ratio of the mass of the sulfonic acrylamide monomer to the total mass of the acrylate monomer and / or methacrylate monomer is 1:(1.5-5), for example, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5 or any value therebetween, preferably 1:(1.5-2.5).

[0024] In some embodiments, the solvent a is selected from one or more of water, alcohols, esters, ketones, aromatic hydrocarbons, and amide solvents. In some embodiments, the solvent a is selected from one or more of water, ethanol, ethyl acetate, acetone, toluene, xylene, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0025] In some embodiments, the polymerization reaction is carried out under the action of a chain transfer agent and / or an initiator. The present invention does not specifically limit the specific types of the chain transfer agent and the initiator, and those skilled in the art can select from commonly used chain transfer agents and initiators as needed. In some embodiments, the chain transfer agent includes dodecanethiol. In some embodiments, the initiator includes azobisisobutyronitrile.

[0026] In some embodiments, the polymerization reaction temperature is 50-90°C.

[0027] In a second aspect, the present invention provides a color paste comprising a pigment, a solvent b and a dispersant, wherein the dispersant comprises the polymer dispersant described in the first aspect of the present invention.

[0028] In some embodiments, the pigment includes one or more of a red pigment, a green pigment, a blue pigment, and a black pigment.

[0029] The red pigment of the present invention includes but is not limited to PR122 red. The blue pigment of the present invention includes but is not limited to A4R blue 15:1. The green pigment of the present invention includes but is not limited to BASF K8730 green. The black pigment of the present invention includes but is not limited to Mitsubishi carbon black MA100.

[0030] In some embodiments, the solvent b is selected from water or an organic solvent, preferably water or an ester organic solvent such as propylene glycol methyl ether acetate.

[0031] In some embodiments, the mass of the polymer dispersant is 1-8% of the mass of the pigment, such as 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or any value therebetween.

[0032] In some embodiments, the dispersant further comprises other dispersants. The present invention does not specifically limit the specific type of the other dispersants. In some embodiments, the other dispersants are selected from BYK9076 and / or BYK2012.

[0033] In some embodiments, the color paste further includes a synthetic resin, and the synthetic resin is a resin having an acidic group. In some embodiments, the synthetic resin is a polyacrylate or polymethacrylate having a carboxylic acid group. In some embodiments, the synthetic resin is at least one of hydroxyethyl methacrylate, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymer.

[0034] In some embodiments, the pigment accounts for 1-30% of the total mass of the color paste, for example 1%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 30% or any value therebetween.

[0035] In some embodiments, the synthetic resin accounts for 1-20% of the total mass of the color paste, such as 1%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or any value therebetween.

[0036] In some embodiments, the polymer dispersant accounts for 0.01% to 1% of the total mass of the color paste, for example 0.01%, 0.05%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.7%, 0.8%, 0.9%, 1% or any value therebetween.

[0037] In some embodiments, the other dispersants account for 1% to 5% of the total mass of the color paste, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% or any value therebetween.

[0038] In some embodiments, the solvent b accounts for 65% to 85% of the total mass of the color paste, for example 65%, 68%, 70%, 72%, 75%, 78%, 80%, 85% or any value therebetween.

[0039] In some embodiments, the color paste includes, by weight percentage: 1-30% pigment, 1% to 20% synthetic resin, 0.01% to 1% polymer dispersant, 1% to 5% other dispersants, and 65% to 85% solvent b.

[0040] In some preferred embodiments, the color paste includes, by weight percentage: 5-20% pigment, 5% to 15% synthetic resin, 0.1% to 0.5% polymer dispersant, 1% to 3% other dispersants, and 70% to 80% solvent b.

[0041] In a third aspect, the present invention provides a photoresist, the raw materials of which include the color paste described in the second aspect of the present invention, an acrylate monomer, a photoinitiator, a coupling agent and a solvent c.

[0042] In some embodiments, the acrylate monomer includes an acrylate monomer with a functionality of ≥ 3. In some embodiments, the acrylate monomer includes dipentaerythritol hexaacrylate and / or pentaerythritol acrylate.

[0043] In some embodiments, the photoinitiator includes an oxime ester compound. In some embodiments, the photoinitiator includes an oxime ester compound having a diphenyl sulfide skeleton or having a fluorene skeleton or having a carbazole skeleton. In some embodiments, the photoinitiator includes 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyloxime) (trade name OXE-01, manufactured by BASF), TR-PBG-3057 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-O-acetyloxime ketone (trade name "ADEKAARKLS NCI-831", manufactured by ADEKA), 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, bis(2,6-difluoro-3-pyrrolophenyl)titanocene or more thereof.

[0044] In some embodiments, the coupling agent includes a silane coupling agent. The silane coupling agent of the present invention includes but is not limited to silane coupling agent 4011, silane coupling agent KH550, silane coupling agent KH570, and the like.

[0045] In some embodiments, the solvent c comprises at least one of an ester solvent, an aromatic hydrocarbon solvent and a halogenated alkane solvent. In some embodiments, the solvent c comprises at least one of propylene glycol monomethyl ether acetate, benzene, toluene, xylene and tetrachloroethane.

[0046] In some embodiments, the color paste accounts for 20% to 40% of the total mass of the photoresist raw material, for example 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40% or any value therebetween.

[0047] In some embodiments, the acrylate monomer accounts for 10% to 20% of the total mass of the photoresist raw material, for example, 10%, 12%, 14%, 15%, 16%, 18%, 20% or any value therebetween.

[0048] In some embodiments, the coupling agent accounts for 0.1% to 0.5% of the total mass of the photoresist raw material, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5% or any value therebetween.

[0049] In some embodiments, the photoinitiator accounts for 0.5% to 2% of the total mass of the photoresist raw material, for example 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2% or any value therebetween.

[0050] In some embodiments, the solvent c accounts for 40% to 60% of the total mass of the photoresist raw material, for example 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60% or any value therebetween.

[0051] In some embodiments, the raw materials of the photoresist include, by weight percentage: 20% to 40% color paste, 10% to 20% acrylate monomer, 0.1% to 0.5% coupling agent, 0.5% to 2% photoinitiator, and 40% to 60% solvent c.

[0052] In some preferred embodiments, the raw materials of the photoresist include, by weight percentage: 25% to 38% color paste, 10% to 15% acrylate monomer, 0.2% to 0.5% coupling agent, 0.5% to 1.5% photoinitiator, and 50% to 60% solvent c.

[0053] In some preferred embodiments, the raw materials of the photoresist include, by weight percentage: 25% to 35% color paste, 10% to 15% acrylate monomer, 0.2% to 0.5% coupling agent, 0.5% to 1.5% photoinitiator, and 50% to 60% solvent c.

[0054] In a fourth aspect, the present invention provides the use of the polymer dispersant described in the first aspect or the color paste described in the second aspect in printing ink, nail polish, PCB solder mask ink, photoresist, and coating.

[0055] Compared with the prior art, the polymer dispersant containing sulfonic acid groups provided by the present invention has both pigment affinity and solvent affinity and is suitable for the preparation of color pastes of different colors. It greatly improves the developing performance of photoresist, especially the clarity and size of the developing. DETAILED DESCRIPTION

[0056] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to constitute any limitation to the present invention.

[0057] The term "C1-C12 alkyl" as used herein refers to a linear or branched chain alkyl group having 1 to 12 carbon atoms, including but not limited to methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, etc. In addition, the alkyl group described in the present invention may be optionally substituted.

[0058] The term "cycloalkyl" as used herein refers to an alkyl group containing at least one ring, and a C4-C12 cycloalkyl group refers to a cyclic alkyl group having 4 to 12 carbon atoms, such as cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like.

[0059] The term "heterocycloalkyl" as used herein includes non-aromatic cyclic groups, including saturated heterocyclic groups having 3-12 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-12 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom. Examples of heterocycloalkyl include oxirane, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxopentanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepineyl and tetrahydrothioxyl. In addition, heterocycloalkyl may be optionally substituted.

[0060] The term "aryl or aromatic group" as used herein includes both non-fused and fused systems. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4'-methylbiphenyl, 4"-tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl and m-quadrenyl. In addition, the aryl group may be optionally substituted.

[0061] As used herein, the term "heteroaryl" includes monocyclic or polycyclic ring systems, such as fused ring systems. C3-C20 heteroaryl includes, but is not limited to, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, furanyl, dibenzofuranyl, benzopyranyl, xanthene, thioxanthenyl, phenothiazine, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinolyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perylene, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenanthrolinyl, oxazinyl, 7-phenanthrenyl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuranyl, 4,7-dibenzofuranyl, 4-methyl-7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiol, 2,7-phenothiol, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl- 5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl , 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinolyl, 6-quinolyl, 2,3-dimethyl-6-quinolyl, 2,3-dimethoxy-6-quinolyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1-methyl-β-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perylene-1-methyl-5-perylene-1-methyl-5-perylene-1-methyl-6-phenanthridinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenazinyl, 10-methyl-2-phenazinyl, and the like. Additionally, heteroaryl groups may be optionally substituted.

[0062] The reagent materials and sources used in the present invention are shown in Table 1.

[0063] Table 1

[0064]

[0065]

[0066] Synthesis Example 1 Preparation of polymer dispersant 1

[0067] Take 2.07g 2-acrylamido-2-methyl-1-propanesulfonic acid, add 3.96g isooctyl methacrylate, 0.164g azobisisobutyronitrile, start the reaction at 60°C, use 6g ethyl acetate and 2g deionized water as solvent, replace with nitrogen, and protect with nitrogen throughout the process. GPC analysis shows that the molecular weight is 30,000.

[0068] Synthesis Example 2 Preparation of polymer dispersant 2

[0069] Take 2.07g of 2-acrylamido-2-methyl-1-propane sulfonic acid, add 3.96g of isooctyl methylpropionate, 0.164g of azobisisobutyronitrile, 0.0606g of dodecanethiol, use 20g of N,N-dimethylformamide as solvent, replace with nitrogen, protect with nitrogen throughout the process, and react at 60℃ for 4h.

[0070] Synthesis Example 3 Preparation of polymer dispersant 3

[0071] Take 2.07g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 1.43g of ethyl dimethylaminoacrylate, 2.22g of isobornyl methacrylate, and 0.164g of azobisisobutyronitrile, add 6g of ethyl acetate and 2g of water as solvent, replace with nitrogen, protect with nitrogen throughout the process, and react at 60°C for 4h.

[0072] Synthesis Example 4 Preparation of Polymer Dispersant 4

[0073] Take 2.07g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 1.43g of ethyl dimethylaminoacrylate, 2.22g of isobornyl methacrylate, 0.164g of azobisisobutyronitrile, add 0.0606g of dodecanethiol, use 20g of N,N-dimethylformamide as solvent, replace with nitrogen, protect with nitrogen throughout the process, and react at 60℃ for 4h.

[0074] Photoresist Examples 1 to 12

[0075] Preparation of black color paste 1 to 4

[0076] The polymer dispersants 1 to 4 prepared in the above-mentioned synthesis examples 1 to 4 were applied to the preparation of carbon black paste: MA100 carbon black pigment, dispersant BYK9076, polymer dispersants 1 to 4, alkali-soluble resin, and PMA were weighed in sequence. Ultrasonic dispersion was performed for 10 minutes, and high-speed shearing was performed at 5000 r / min for 30 minutes and 9000 r / min for 30 minutes to obtain black color pastes 1 to 4, the fineness of which was less than 2 μm in the test, and the specific content of the color paste is shown in Table 2 below.

[0077] Contrast color paste 1

[0078] MA100 carbon black pigment, dispersant BYK9076, alkali-soluble resin and PMA were weighed in sequence. Ultrasonic dispersion was performed for 10 minutes, and high-speed shearing was performed at 5000 r / min for 30 minutes and 9000 r / min for 30 minutes. The fineness test was below 2 μm. The specific contents are shown in Table 2.

[0079] Table 2 Composition of black color paste

[0080]

[0081] Preparation of red color paste 1 to 4

[0082] The polymer dispersants 1 to 4 prepared in the above-mentioned synthesis examples 1 to 4 were used to prepare red color paste: PR122 red pigment, dispersant BYK9076, polymer dispersants 1 to 4, alkali-soluble resin, and PMA were weighed in sequence. Ultrasonic dispersion was performed for 10 minutes, and high-speed shearing was performed at 5000 r / min for 10 minutes and 9000 r / min for 10 minutes to obtain red color pastes 1 to 4, the fineness of which was less than 2 μm in the test, and the specific contents were shown in Table 3 below.

[0083] Contrast color paste 2

[0084] PR122 red pigment, dispersant BYK9076, alkali-soluble resin and PMA were weighed in sequence. Ultrasonic dispersion was performed for 10 min, high-speed shearing was performed at 5000 r / min, 30 min, and 9000 r / min, 30 min, and the fineness test was below 2 μm. The specific contents are shown in Table 3 below.

[0085] Table 3 Red color paste composition

[0086]

[0087] The alkali-soluble resin used in the above-mentioned black color pastes 1-4, red color pastes 1-4 and comparative color pastes 1-2 was synthesized by the following method: 6 parts of hydroxyethyl methacrylate, 18 parts of benzyl methacrylate, 6 parts of methacrylic acid, 0.6 parts of dodecanethiol and 200 parts of toluene were weighed in sequence and added into a three-necked flask, and a mixed solution of 1.5 parts of azobisisobutyronitrile and toluene was added dropwise into the flask, the mixture was added dropwise for 1 hour, the reaction was continued for 5 hours, and a white solid product was obtained by cooling and filtering.

[0088] Synthesis of photoresist

[0089] The above black color pastes 1-4, red color pastes 1-4 and comparative color pastes 1-2 are used for the preparation of photoresist. After weighing the materials according to the ratio in Table 4, ultrasonic dispersion is performed for 3 minutes, and high-speed shear is performed at 5000r / min for 3 minutes, and then the photoresist samples can be used for preparation.

[0090] Table 4 Photoresist composition

[0091]

[0092]

[0093] Sample preparation and testing

[0094] Sample preparation: The above-mentioned photoresist embodiments 1 to 12 and photoresist comparative examples 1 to 3 were evenly coated on a glass slide using an 8 μm wire rod, dried in a vacuum oven at 80°C for 5 min, cooled to room temperature and exposed (exposure conditions are shown in Table 5 below), developed (developed in a 0.5% Na2CO3 aqueous solution for 20 s, taken out and rinsed in clean water for 5 s), dried (dried in a vacuum oven at 80°C for 5 min), and cooled to room temperature.

[0095] Table 5 Exposure conditions

[0096]

[0097] Sample test: The images of the samples were observed and measured using an electron optical microscope. The results are shown in Tables 6 and 7 below. The larger the value, the higher the sensitivity.

[0098] Table 6 Black photoresist sample test results

[0099]

[0100]

[0101] Table 7 Red photoresist sample test results

[0102]

[0103] As can be seen from Table 6, the comparison between photoresist examples 1 to 4 and photoresist comparative example 1 shows that the developed sizes of photoresist examples 1 to 4 of the present invention are all higher than those of photoresist comparative example 1; the comparison between photoresist examples 5 to 8 and photoresist comparative example 2 shows that the developed sizes of photoresist examples 5 to 8 of the present invention are all higher than those of photoresist comparative example 2. This indicates that the addition of the polymer dispersant of the present invention to the black color paste significantly improves the developed size of the photoresist, especially the addition of photoresist example 6 has the greatest improvement in the developed size of the photoresist.

[0104] As can be seen from Table 7, the comparison between photoresist examples 9 to 12 and photoresist comparative example 3 shows that the developed sizes of photoresist examples 9 to 12 of the present invention are all higher than that of photoresist comparative example 3. This indicates that the addition of the polymer dispersant of the present invention to the red color paste significantly improves the developed size of the photoresist, especially the polymer dispersant 3 used in photoresist example 11 under the action of photoinitiator 831, which has the most obvious improvement on the developed size of the red photoresist.

[0105] In summary, the polymer dispersant of the present invention can significantly improve the development size and image clarity of black or red photoresist.

[0106] The technical solution of the present invention is not limited to the above-mentioned specific embodiments. All technical variations made according to the technical solution of the present invention fall within the protection scope of the present invention.

Claims

1. A polymer dispersant comprising a copolymer of a sulfonic acid acrylamide monomer and an acrylate monomer and / or a methacrylate monomer.

2. The polymer dispersant according to claim 1, characterized in that The sulfonic acid acrylamide monomer has a structure represented by formula I, In Formula I, R1 represents C1-C12 alkylene, C4-C12 cycloalkylene, C3-C12 heterocycloalkylene, C6-C20 arylene or C3-C20 heteroarylene, preferably C1-C6 alkylene or C6-C12 arylene, more preferably C2-C4 alkylene and phenylene, further preferably methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene and phenylene; Preferably, the sulfonic acid acrylamide monomer includes 2-acrylamido-2-methyl-1-propanesulfonic acid and / or 2-acrylamidoethanesulfonic acid.

3. The polymer dispersant according to claim 1 or 2, characterized in that The acrylic acid ester monomers include esters formed by acrylic acid and one or more selected from C1-C12, preferably C4-C12, fatty alcohols, C1-C12, preferably C4-C12, alicyclic alcohols, and C6-C12 aromatic alcohols; and / or, The methacrylate monomers include esters formed by methacrylic acid and one or more selected from C1-C12, preferably C4-C12, fatty alcohols, C1-C12, preferably C4-C12, alicyclic alcohols, and C6-C12 aromatic alcohols; Optionally, the methacrylate monomer and the acrylate monomer further contain a dialkylamine functional group; Preferably, the acrylic acid ester monomer includes one or more of isobornyl acrylate, benzyl acrylate, isooctyl acrylate, butyl acrylate, dimethylaminoethyl acrylate, and 2-ethylhexyl acrylate; Preferably, the methacrylate monomers include one or more of isobornyl methacrylate, benzyl methacrylate, isooctyl methacrylate, butyl methacrylate, dimethylaminoethyl methacrylate, and 2-ethylhexyl methacrylate.

4. The polymer dispersant according to any one of claims 1 to 3, characterized in that The preparation of the copolymer comprises the following steps: Allowing the sulfonic acrylamide monomer to polymerize with the acrylate monomer and / or methacrylate monomer in solvent a; Preferably, the ratio of the mass of the sulfonic acrylamide monomer to the total mass of the acrylate monomer and / or methacrylate monomer is 1:(1.5-5); Preferably, the solvent a is selected from one or more of water, alcohols, esters, ketones, aromatic hydrocarbons, and amide solvents, preferably one or more of water, ethanol, ethyl acetate, acetone, toluene, xylene, N,N-dimethylformamide, and N,N-dimethylacetamide; Preferably, the polymerization reaction is carried out under the action of a chain transfer agent and / or an initiator, wherein the chain transfer agent preferably comprises dodecanethiol, and the initiator preferably comprises azobisisobutyronitrile; Preferably, the polymerization reaction temperature is 50-90°C.

5. A color paste comprising a pigment, a solvent b and a dispersant, wherein the dispersant comprises the polymer dispersant according to any one of claims 1 to 4.

6. The color paste according to claim 5, characterized in that: The pigment includes one or more of a red pigment, a green pigment, a blue pigment and a black pigment; preferably, the red pigment includes PR122 red, the blue pigment includes A4R blue 15:1, the green pigment includes BASF K8730 green, and the black pigment includes Mitsubishi carbon black MA100; The solvent b is selected from water or an ester organic solvent, preferably water or propylene glycol methyl ether acetate; Preferably, the mass of the polymer dispersant is 1-8% of the mass of the pigment; Optionally, the dispersant further comprises other dispersants, preferably, the other dispersants are selected from BYK9076 and / or BYK2012; Optionally, the color paste also includes a synthetic resin, which is a resin having an acidic group, preferably a polyacrylate or polymethacrylate having a carboxylic acid group, and more preferably at least one of hydroxyethyl methacrylate, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and methacrylic acid copolymer, benzyl methacrylate and methacrylic acid copolymer, methyl methacrylate and butyl methacrylate, and methacrylic acid and styrene copolymer.

7. The color paste according to claim 5 or 6, characterized in that: In terms of weight percentage, the color paste includes: 1-30% pigment, 1% to 20% synthetic resin, 0.01% to 1% polymer dispersant, 1% to 5% other dispersants, and 65% to 85% solvent b; Preferably, in terms of weight percentage, the color paste comprises: 5-20% pigment, 5% to 15% synthetic resin, 0.1% to 0.5% polymer dispersant, 1% to 3% other dispersants, and 70% to 80% solvent b.

8. A photoresist, the raw materials of which include the color paste according to any one of claims 5 to 7, an acrylate monomer, a photoinitiator, a coupling agent and a solvent c; Preferably, the acrylate monomer comprises an acrylate monomer with a functionality ≥ 3, more preferably dipentaerythritol hexaacrylate and / or pentaerythritol acrylate; Preferably, the photoinitiator includes an oxime ester compound, preferably an oxime ester compound having a diphenyl sulfide skeleton, a fluorene skeleton, or a carbazole skeleton, more preferably 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzoyl oxime), TR-PBG-3057, (9-ethyl-6-nitro-9H-carbazole-3-yl)[4-(2-methoxy-1-methylethoxy-2-methylphenyl]-O-acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino- One or more of 2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene; Preferably, the coupling agent includes one or more of silane coupling agent KH550, silane coupling agent KH570, and silane coupling agent 4011, preferably includes silane coupling agent 4011; Preferably, the solvent c comprises at least one of an ester solvent, an aromatic hydrocarbon solvent and a halogenated alkane solvent, preferably at least one of propylene glycol monomethyl ether acetate, benzene, toluene, xylene and tetrachloroethane.

9. The photoresist according to claim 8, characterized in that The raw materials include, by weight percentage: 20% to 40% of color paste, 10% to 20% of acrylate monomer, 0.1% to 0.5% of coupling agent, 0.5% to 2% of photoinitiator, and 40% to 60% of solvent c; Preferably, the raw materials include, by weight percentage: 25% to 38% of color paste, 10% to 15% of acrylate monomers, 0.2% to 0.5% of coupling agent, 0.5% to 1.5% of photoinitiator, and 50% to 60% of solvent c.

10. Use of the polymer dispersant according to any one of claims 1 to 4 or the color paste according to any one of claims 5 to 7 in printing ink, nail polish, PCB solder mask ink, photoresist, and coating.

Images