CN116144029A - Organosilicon leveling agent, preparation method thereof, black matrix photosensitive resin composition, color filter and liquid crystal display device - Google Patents

Organosilicon leveling agent, preparation method thereof, black matrix photosensitive resin composition, color filter and liquid crystal display device Download PDF

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CN116144029A
CN116144029A CN202310074713.1A CN202310074713A CN116144029A CN 116144029 A CN116144029 A CN 116144029A CN 202310074713 A CN202310074713 A CN 202310074713A CN 116144029 A CN116144029 A CN 116144029A
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bis
acid
hydroxy
black matrix
photosensitive resin
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陈谦
郑雪峰
谢羽
黄常刚
王雪岚
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Fuyang Sineva Material Technology Co Ltd
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Fuyang Sineva Material Technology Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds

Abstract

The application provides an organosilicon leveling agent, a preparation method thereof and black matrix sensitizationResin composition, color filter and liquid crystal display device, relates to the material field. The structural general formula of the organic silicon leveling agent is as follows:
Figure DDA0004065775240000011
the preparation method comprises the following steps: reacting a siloxane compound with furan-containing cyclopropene ester in the presence of a catalyst and a polymerization inhibitor, and adding a propenyl polyether compound to react after finishing; and after the reaction is finished, regulating the pH value of the system to hydrolyze the silicon ether to obtain silanol, and then dropwise adding acryloyl chloride to react to obtain the organosilicon leveling agent. The black matrix photosensitive resin composition includes a silicone leveling agent. The raw material of the color filter includes a black matrix photosensitive resin composition. The liquid crystal display device includes color filtering. The organosilicon leveling agent provided by the application can provide excellent leveling effect in the photoresist of the high-concentration black pigment, and can still provide good leveling effect after development, so that the defects of poor roughness and uniformity of a coating film in the post-baking process are reduced.

Description

Organosilicon leveling agent, preparation method thereof, black matrix photosensitive resin composition, color filter and liquid crystal display device
Technical Field
The application relates to the field of materials, in particular to an organosilicon leveling agent and a preparation method thereof, a black matrix photosensitive resin composition, a color filter and liquid crystal display equipment.
Background
The color filter is a key device for realizing color display of a TFT-LCD (thin film transistor liquid crystal display), and is generally formed by coating black photoresist on the surface of a transparent substrate such as glass to form a black matrix, and sequentially forming pixels of different colors of photoresist such as R, G, B in a lattice-like, stripe-like or like pattern. Among them, the black matrix BM can prevent R, G, B color pixels from being mixed with each other and block and absorb internal and external light to maintain the necessary color saturation and contrast of the color filter, which requires the BM to have high shade. In order to achieve the target shade with a film thickness as small as possible, it is common to increase the proportion of black pigment in the black matrix photosensitive resin composition, which accordingly causes the other components than the black pigment to be reduced, resulting in the following problems: the viscosity is improved, the coating property is poor, the thickness of the coating film is uneven, and the surface is rough.
Leveling agents are effective means for solving the above problems, and polyether modified silicone leveling agents are often used in the prior art. For example, CN112111065a discloses a polyether modified organosilicon leveling agent structure and a preparation method thereof, which have good defoaming and foam inhibiting functions when applied to water-based paint, and have excellent performances of no cracking, no stickiness and no shrinkage cavity, but are not applicable to organic systems. CN105315757B discloses a polyether polyester modified organosilicon leveling agent structure and a preparation method thereof, and the leveling agent can effectively reduce surface tension in both organic paint and water paint and provide good leveling property. In addition, CN112831003B discloses a polyether modified organosilicon leveling agent with an anchoring group and a fluorocarbon side chain and a preparation method thereof, and the polyether modified organosilicon leveling agent is prepared from allyl polyether, fluoroacrylate, acrylamide and hydrogen-containing silicone oil through hydrosilylation reaction. The leveling agent has good affinity to pigment, obvious leveling effect and can effectively eliminate shrinkage cavities.
The current leveling agent for photoresist has the following action principle: the leveling agent is enriched on the surface of the photoresist solution, the surface tension is reduced, and the spreadability of a coating film is increased, but the leveling agent enriched on the surface is easy to wash away together in the developing process, and only a small amount of residues remain after development, so that the leveling effect of the conventional leveling agent after development is greatly reduced, and the surface roughness is difficult to eliminate in the post-baking process.
Therefore, there is a need to develop a material that still provides an effective leveling effect during post-bake flow.
Disclosure of Invention
The purpose of the present application is to provide an organosilicon leveling agent and a preparation method thereof, a black matrix photosensitive resin composition, a color filter and a liquid crystal display device, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
an organosilicon leveling agent has a structural general formula:
Figure BDA0004065775200000021
wherein a is any integer from 4 to 30, b is any integer from 0 to 10, m is any integer from 4 to 20, n is any integer from 2 to 10, and p is any integer from 4 to 20.
Preferably, m is any integer from 4 to 10, n is any integer from 2 to 6, and p is any integer from 4 to 10;
preferably, m: n: p=4: 2:4 or m: n: p=8: 4:8.
the application also provides a preparation method of the organic silicon leveling agent, which comprises the following steps:
the method comprises the steps of (1) carrying out a first reaction on siloxane compounds and benzofuran cyclopropene grease in the presence of a catalyst and a polymerization inhibitor, and adding propenyl polyether compounds to carry out a second reaction after finishing the first reaction;
and after the second reaction is finished, regulating the pH value of the system to hydrolyze the silicon ether to obtain silanol, and then dropwise adding acryloyl chloride to perform a third reaction to obtain the organosilicon leveling agent.
Preferably, the siloxane-based compound comprises siloxane C 20 H 65 O 13 Si 12 And/or siloxane C 34 H 113 O 23 Si 22 ；
Preferably, the propenyl polyether compound comprises propenyl polyether C 49 H 98 O 21 ；
Preferably, the catalyst comprises chloroplatinic acid;
preferably, the polymerization inhibitor comprises hydroquinone.
The application also provides a black matrix photosensitive resin composition, which comprises the organosilicon leveling agent;
preferably, the silicone leveling agent is used in an amount of 0.01wt% to 1wt%, preferably 0.01wt% to 0.2wt% of the total solid content mass of the black matrix photosensitive resin composition.
Preferably, the black matrix photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, a colorant, and a solvent;
preferably, the black matrix photosensitive resin composition further comprises a curing accelerator, a coupling agent, an antioxidant, a polymerization inhibitor, a defoaming agent; the coupling agent is preferably a silane coupling agent.
Preferably, the alkali-soluble resin is used in an amount of 10wt% to 30wt% based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the alkali-soluble resin includes a resin having a hydroxyl group, a carboxyl group, a phosphate group, a sulfonate group, preferably a carboxyl group, more preferably both an ethylenically unsaturated group and a carboxyl group;
preferably, the alkali-soluble resin comprises a fluorene-based resin, preferably a bisphenol fluorene-based resin;
preferably, the bisphenol fluorene resin is one or more of unsaturated group-containing photosensitive resins obtained by reacting a reactant of an epoxy compound derived from bisphenol fluorene and having two glycidyl ether groups with (meth) acrylic acid with a polycarboxylic acid or an anhydride thereof;
preferably, the bisphenol fluorene derivative epoxy compound with two glycidyl ether groups has a structural general formula:
Figure BDA0004065775200000041
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and x and y are each independently 0 or 1;
preferably, the bisphenol fluorene-derived epoxy compound with two glycidyl ether groups is obtained by etherification reaction of bisphenol compound and haloalkoxy compound;
preferably, the bisphenol compound includes bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3, 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2-hydroxy-2-chlorophenyl) propane, 2-bis (4-hydroxyphenyl) ether, 2-hydroxy-2-chlorophenyl) ether, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene one or more of 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4 '-biphenol, 3' -biphenol; bisphenol compounds having fluorene-9, 9-diyl are preferred;
preferably, the polycarboxylic acid or anhydride thereof comprises succinic acid, acetyl succinic acid, maleic acid, adipic acid, iconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, side-oxoglutarate, pimelic acid, sebacic acid, suberic acid, diglycolic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, or monoanhydride thereof;
preferably, the bisphenol fluorene resin has an average molecular weight M w 4000-20000, acid value of 30-200 mgKOH/g; more preferably, the bisphenol fluorene resin has an average molecular weight M w 4000-8000, and an acid value of 30-100 mgKOH/g.
Preferably, the amount of the photopolymerizable monomer is 5wt% to 25wt% based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the photopolymerization monomer is selected from one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate and ethylene oxide modified dipentaerythritol hexaacrylate; preferably polydipentaerythritol hexaacrylate;
preferably, the photoinitiator is used in an amount of 0.5wt% to 5wt% based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the photoinitiator is selected from one or more of benzoin derivatives, benzil derivatives, dialkoxyacetophenones, alpha-hydroxyalkyl phenones, alpha-aminoalkylphenones, acyl phosphine oxides, oxime esters, benzoyl formate, benzophenone, thioxanthone, camphorquinone; oxime ester compounds are preferred;
preferably, the colorant is used in an amount of 30wt% to 60wt% based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the black matrix photosensitive resin composition is cured to form a photoresist film having an optical density of not less than 3.8 in a film thickness of 1 μm;
preferably, the colorant is a carbon black pigment, and is obtained by mixing and grinding raw materials including carbon black, a dispersing agent, a dispersing resin and a solvent, and then adding the solvent for dilution;
preferably, the solvent is used in an amount of 60wt% to 85wt% based on the total mass of the black matrix photosensitive resin composition;
preferably, the solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl ethoxypropionate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol diacetate; propylene glycol methyl ether acetate is preferred.
The application also provides a color filter, and the raw material of the color filter comprises the black matrix photosensitive resin composition.
The application also provides a liquid crystal display device comprising the color filter.
Compared with the prior art, the beneficial effects of this application include:
the end group of the organosilicon leveling agent contains unsaturated double bonds, and the side chain of the organosilicon leveling agent is generated by copolymerizing allyl polyether and benzofuran-containing cyclopropene; can effectively reduce the surface tension and enhance the coating property. Still providing good coating properties at high carbon black concentrations; the organic silicon leveling agent has unsaturated double bond to form weak cross-linking during exposure, and the leveling agent is not washed off during development, so that the leveling effect can be provided during post-baking, and the problems of rough surface and uneven film thickness are effectively solved.
The black matrix photosensitive resin composition provided by the application can provide a black matrix with smooth surface and excellent film thickness uniformity.
The color filter and the liquid crystal display device provided by the application are high in yield and stable and excellent in product quality.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 example 1 composition A1 GPC test chart;
FIG. 2 example 2 composition A2 GPC test chart;
FIG. 3 example 3 composition A3 GPC test chart;
FIG. 4 example 6 contact angle test chart;
FIG. 5 example 7 contact angle test chart;
FIG. 6 is a graph of comparative example 1 contact angle test;
fig. 7 is a graph of comparative example 2 contact angle test.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such 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 claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
An organosilicon leveling agent has a structural general formula:
Figure BDA0004065775200000081
wherein C is 2 H 4 The degree of polymerization a of the O-structure (hereinafter referred to as EO) is an arbitrary integer of 4 to 30, C 3 H 6 The polymerization degree b of the O-structure (hereinafter referred to as PO) is any integer from 0 to 10, m is any integer from 4 to 20, n is any integer from 2 to 10, and p is any integer from 4 to 20.
In an alternative embodiment, m is any integer from 4 to 10, n is any integer from 2 to 6, and p is any integer from 4 to 10;
in an alternative embodiment, m: n: p=4: 2:4 or m: n: p=8: 4:8.
alternatively, a may be any one of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, b may be any one of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, m may be any one of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, n may be any one of 2, 3, 4, 5, 6, 7, 8, 9, 10, p may be any one of 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.
The application also provides a preparation method of the organic silicon leveling agent, which comprises the following steps:
the method comprises the steps of (1) carrying out a first reaction on siloxane compounds and benzofuran cyclopropene grease in the presence of a catalyst and a polymerization inhibitor, and adding propenyl polyether compounds to carry out a second reaction after finishing the first reaction;
and after the second reaction is finished, regulating the pH value of the system to hydrolyze the silicon ether to obtain silanol, and then dropwise adding acryloyl chloride to perform a third reaction to obtain the organosilicon leveling agent.
The reaction equation is shown below:
Figure BDA0004065775200000101
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in an alternative embodiment, the siloxane-based compound comprises siloxane C 20 H 65 O 13 Si 12 And/or siloxane C 34 H 113 O 23 Si 22 ；
In an alternative embodiment, the propenyl polyether compound comprises propenyl polyether C 49 H 98 O 21 ；
In an alternative embodiment, the catalyst comprises chloroplatinic acid;
in an alternative embodiment, the polymerization inhibitor comprises hydroquinone.
The application also provides a black matrix photosensitive resin composition, which comprises the organosilicon leveling agent;
in an alternative embodiment, the silicone leveling agent is used in an amount of 0.01wt% to 1wt%, preferably 0.01wt% to 0.2wt% of the total solid content mass of the black matrix photosensitive resin composition.
Alternatively, the silicone leveling agent may be used in an amount of any one of 0.01wt%, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, or 0.01wt% -1wt% of the mass of the entire solid components of the black matrix photosensitive resin composition.
In an alternative embodiment, the black matrix photosensitive resin composition further includes an alkali-soluble resin, a photopolymerization monomer, a photoinitiator, a colorant, and a solvent;
in an alternative embodiment, the black matrix photosensitive resin composition further includes a curing accelerator, a coupling agent, an antioxidant, a polymerization inhibitor, a defoaming agent; the coupling agent is preferably a silane coupling agent.
In an alternative embodiment, the alkali-soluble resin is used in an amount of 10wt% to 30wt% of the total solid content mass of the black matrix photosensitive resin composition;
alternatively, the alkali-soluble resin may be used in an amount of any one of 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, or 10wt% to 30wt% of the total solid content mass of the black matrix photosensitive resin composition;
in an alternative embodiment, the alkali-soluble resin comprises a resin having hydroxyl groups, carboxyl groups, phosphate groups, sulfonate groups, preferably having carboxyl groups, more preferably having both ethylenically unsaturated groups and carboxyl groups;
in order to dissolve the unexposed portions in an alkali developer, but not to retain the unexposed portions during the development process, it is generally required that the solubility of the exposed portions and the unexposed portions with respect to the alkali developer is changed after the resin composition coating film is exposed.
In an alternative embodiment, the alkali-soluble resin comprises a fluorene-based resin, preferably a bisphenol fluorene-based resin;
the fluorene resin may be obtained by purchasing commercially available products, or may be prepared by a known method, for example, the method disclosed in Japanese patent application laid-open No. 8-278629, and the method disclosed in China, such as CN 106397752B.
In an alternative embodiment, the bisphenol fluorene resin is one or more of unsaturated group-containing photosensitive resins obtained by reacting a reactant of an epoxy compound derived from bisphenol fluorene and having two glycidyl ether groups with (meth) acrylic acid with a polycarboxylic acid or anhydride thereof;
the term "(meth) acrylic acid" refers to a combination of acrylic acid and methacrylic acid, and may refer to either or both of them.
In an alternative embodiment, the bisphenol fluorene derived epoxy compound having two glycidyl ether groups has the general structural formula:
Figure BDA0004065775200000121
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and x and y are each independently 0 or 1;
in an alternative embodiment, the bisphenol fluorene-derived epoxy compound having two glycidyl ether groups is obtained by etherification of a bisphenol compound with a haloalkoxy compound;
in an alternative embodiment, the bisphenol compound comprises bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3, 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxy-3, 5-chlorophenyl) propane, 2-bis (4-hydroxy-chlorophenyl) ether, 2, 4-hydroxy-2-chlorophenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) ether Bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene one or more of 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4 '-biphenol, 3' -biphenol; bisphenol compounds having fluorene-9, 9-diyl are preferred;
in an alternative embodiment, the polycarboxylic acid or anhydride thereof comprises succinic acid, acetylsuccinic acid, maleic acid, adipic acid, iconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, pendant oxoglutarate, pimelic acid, sebacic acid, suberic acid, diglycolic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, or monoanhydrides thereof;
in an alternative embodiment, the bisphenol fluorene-based resin is averagedMolecular weight M w 4000-20000, acid value of 30-200 mgKOH/g; more preferably, the bisphenol fluorene resin has an average molecular weight M w 4000-8000, and an acid value of 30-100 mgKOH/g.
In an alternative embodiment, the photopolymerizable monomer is used in an amount of 5wt% to 25wt% based on the total solid content mass of the black matrix photosensitive resin composition;
alternatively, the amount of the photopolymerizable monomer may be 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, or any value between 5wt% and 25wt% of the total solid content mass of the black matrix photosensitive resin composition;
in an alternative embodiment, the photopolymerizable monomer is selected from one or more of pentaerythritol triacrylate (abbreviated as PETA, CAS number 3524-68-3), pentaerythritol tetraacrylate (abbreviated as PETTA, CAS number 4986-89-4), polydipentaerythritol pentaacrylate (abbreviated as DPEPA, CAS number 60506-81-2), polydipentaerythritol hexaacrylate (abbreviated as DPHA, CAS number 29570-58-9), ethylene oxide modified dipentaerythritol hexaacrylate (abbreviated as DPEA-12); preferably polydipentaerythritol hexaacrylate;
in an alternative embodiment, the photoinitiator is used in an amount of 0.5wt% to 5wt% of the total solid content mass of the black matrix photosensitive resin composition;
alternatively, the photoinitiator may be used in an amount of any one of 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, or 0.5wt% to 5wt% of the total solid content mass of the black matrix photosensitive resin composition;
in an alternative embodiment, the photoinitiator is selected from one or more of benzoin derivatives, benzil derivatives, dialkoxyacetophenones, alpha-hydroxyalkyl phenones, alpha-aminoalkylphenones, acylphosphine oxides, oxime ester compounds, benzoyl formate, benzophenone, thioxanthone, camphorquinone; oxime ester compounds are preferred;
in an alternative embodiment, the colorant is used in an amount of 30wt% to 60wt% of the total solid content mass of the black matrix photosensitive resin composition;
the colorant is a light-shielding material, and the content thereof is determined according to the required light-shielding degree.
Alternatively, the colorant may be used in an amount of any one of 30wt%, 40wt%, 50wt%, 60wt%, or 30wt% to 60wt% of the total solid content mass of the black matrix photosensitive resin composition;
in an alternative embodiment, the black matrix photosensitive resin composition is cured to form a photoresist film, and the optical density of the film thickness of 1 μm is not less than 3.8;
in an alternative embodiment, the colorant is a carbon black pigment dispersion liquid, and is obtained by mixing and grinding raw materials including carbon black, a dispersing agent, a dispersing resin and a solvent, and adding the solvent for further dilution;
the carbon BLACK can be obtained by purchasing commercially available products, and specific examples thereof include DIAGRAM BLACK II, DIAGRAMBLACK N339, DIAGRAM BLACK SH, DIAGRAM BLACK H, DIAGRAM LH, DIAGRAM HA, DIAGRAM SF, DIAGRAM N550M, DIAGRAM E, DIAGRAM G, DIAGRAM R, DIAGRAM N760M, DIAGRAM LR, #2700, #2600, #2350, #2300, #2200, #1000, #980, #900, MCF88, #52, #50, #47, #45L, #25, # CF9, #95, #3030, #3050, MA7, MA77, MA8, MA11, OIL7B, OIL9B, OIL11B, OIL B and OIL31B (manufactured by Mitsubishi Chemical Corporation); PRINTEX-U, PRINTEX-V, PRINTEX-140U, PRINTEX-140V, PRINTEX-95, PRINTEX-85, PRINTEX-75, PRINTEX-55, PRINTEX-45, PRINTEX-300, PRINTEX-35, PRINTEX-25, PRINTEX-200, PRINTEX-40, PRINTEX-30, PRINTEX-3, PRINTEX-A, SPECIAL BLACK-550, SPECIALBLACK-350, SPECIAL BLACK-250, SPECIAL BLACK-100, and LAMP BLACK-101 (produced by Degussa Japan Co., ltd.; they may be used alone or in combination.
In an alternative embodiment, the solvent is used in an amount of 60wt% to 85wt% of the total mass of the black matrix photosensitive resin composition;
alternatively, the solvent may be used in an amount of any one of 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, or 60wt% to 85wt% of the total mass of the black matrix photosensitive resin composition;
in an alternative embodiment, the solvent is selected from one or more of PMA (propylene glycol methyl ether acetate), PM (propylene glycol methyl ether), EEP (ethyl ethoxypropionate), DPMA (dipropylene glycol methyl ether acetate), 3MBA (3-methoxybutyl acetate), DBDG (diethylene glycol dibutyl ether), DMDG (diethylene glycol dimethyl ether), EDM (diethylene glycol methyl ethyl ether), PGDA (propylene glycol diacetate); propylene glycol methyl ether acetate is preferred.
The application also provides a color filter, and the raw material of the color filter comprises the black matrix photosensitive resin composition.
The application also provides a liquid crystal display device comprising the color filter.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides an organosilicon leveling agent, and the preparation method thereof is as follows:
into a four-necked flask, 8.50g of siloxane C was charged 20 H 65 O 13 Si 12 (m: n: p=4:2:4), 3.76g benzofuran cyclopropene ester C 11 H 8 O 3 Adding chloroplatinic acid catalyst (2 wt% solution of chloroplatinic acid in isopropanol) and polymerization inhibitor (hydroquinone), keeping nitrogen for 10min, stirring at a rotating speed of 150-200 r/min, heating to 80 ℃, reacting at constant temperature for 6h, and heating to 120 ℃ after the reaction is completed. Catalyst and polymerization inhibitor were added and 40.92g of propenyl polyether C was added dropwise 49 H 98 O 21 (EO/po=15:5), the reaction was continued at a constant temperature of 120 ℃ for 4 hours, and then the temperature was naturally lowered to room temperature. After the flask cooled to room temperature, an ice bath was preparedKeeping the temperature range between 0 and 5 ℃, slowly adjusting the pH value of malonic acid to be between 5 and 6 with weak acidity, promoting the hydrolysis of the silyl ether to silanol, and continuously dropwise adding 1.8g of acryloyl chloride. After the completion of the dropwise addition, slow heating was started, and after reaching 40 ℃, the temperature was maintained for reaction for 3 hours. Cooling, decompressing to remove low-boiling-point substances, purifying the product and obtaining the modified organic silicon A1.
The modified silicone A1 was confirmed by mass spectrometry and GPC: MS (m/z): 5369M + The method comprises the steps of carrying out a first treatment on the surface of the GPC measurement of weight average molecular weight M w ＝5997。
GPC chart of example 1 composition A1 is shown in FIG. 1.
Example 2
The embodiment provides an organosilicon leveling agent, and the preparation method thereof is as follows:
into a four-necked flask, 15.08g of siloxane C was charged 34 H 113 O 23 Si 22 (m: n: p=8:4:8), 7.52g benzofuran cyclopropene ester C 11 H 8 O 3 Adding chloroplatinic acid catalyst (2 wt% solution of chloroplatinic acid in isopropanol) and polymerization inhibitor (hydroquinone), keeping nitrogen for 10min, stirring at a rotating speed of 150-200 r/min, heating to 90 ℃, reacting at constant temperature for 8h, and heating to 120 ℃ after the reaction is completed. Adding catalyst and polymerization inhibitor, and dripping 81.84g of propenyl polyether C 49 H 98 O 21 (EO/po=15:5), the reaction was continued at a constant temperature of 120 ℃ for 8 hours, and then the temperature was naturally lowered to room temperature. After the flask is cooled to room temperature, an ice bath is prepared, the temperature range is kept at 0-5 ℃, the pH is slowly adjusted to be slightly acidic to 5-6 by malonic acid, the hydrolysis of the silyl ether to silanol is promoted, and 1.8g of acryloyl chloride is continuously added dropwise. After the completion of the dropwise addition, slow heating was started, and after reaching 40 ℃, the temperature was maintained for reaction for 3 hours. Cooling, decompressing to remove low-boiling-point substances, purifying the product and obtaining the modified organic silicon A2.
The modified silicone A2 was confirmed by mass spectrometry and GPC: MS (m/z): 10493M + The method comprises the steps of carrying out a first treatment on the surface of the GPC measurement of weight average molecular weight M w ＝11017。
Example 2 a GPC test diagram of the composition A2 is shown in fig. 2.
Example 3
The embodiment provides an organosilicon leveling agent, and the preparation method thereof is as follows:
into a four-necked flask, 15.08g of siloxane C was charged 34 H 113 O 23 Si 22 (m: n: p=8:4:8), 7.52g benzofuran cyclopropene ester C 11 H 8 O 3 Adding chloroplatinic acid catalyst (2 wt% solution of chloroplatinic acid in isopropanol) and polymerization inhibitor (hydroquinone), keeping nitrogen for 10min, stirring at a rotating speed of 150-200 r/min, heating to 90 ℃, reacting at constant temperature for 8h, and heating to 120 ℃ after the reaction is completed. Adding catalyst and polymerization inhibitor, and dripping 87.44g of propenyl polyether C 49 H 98 O 21 (EO/po=10:10), and after keeping the constant temperature of 120 ℃ for 4 hours, the temperature is naturally reduced to room temperature. After the flask is cooled to room temperature, an ice bath is prepared, the temperature range is kept at 0-5 ℃, the pH is slowly adjusted to 5-6 by malonic acid, the hydrolysis of the silyl ether to silanol is promoted, and 1.8g of acryloyl chloride is continuously added dropwise. After the completion of the dropwise addition, slow heating was started, and after reaching 40 ℃, the temperature was maintained for reaction for 3 hours. Cooling, decompressing to remove low-boiling-point substances, purifying the product and obtaining the modified organic silicon A3.
The modified silicone A3 was confirmed by mass spectrometry and GPC: MS (m/z): 11053M + The method comprises the steps of carrying out a first treatment on the surface of the GPC measurement of weight average molecular weight M w ＝12750。
Example 3 a GPC test chart of the composition A3 is shown in fig. 3.
< carbon Black Dispersion liquid >
The carbon black dispersion liquid is homemade Siniva-01, and the components and mass ratio are as follows:
carbon black was MA77 (Mitsubishi Chemical Corporation production): 23.00wt%;
the dispersion resin was V259ME (Nippon steel Chemical Corporation) produced by 5.00%;
the dispersant was BYK-167 (BYK Chemical Corporation) 3.35 wt.%;
the solvent is PMA propylene glycol methyl ether acetate 68.65wt%.
< cardo resin >
As the cardo resin, a mixture of V259ME and propylene glycol methyl ether acetate (manufactured by Nippon steel Chemical Corporation) was used, and the solid content was 56.4% by weight.
< photopolymerizable monomer >
As the photopolymerization monomer, DPHA-polydipentaerythritol hexaacrylate (manufactured by Japanese chemical Co., ltd.) was used.
< oxime ester initiator >
As photoinitiator, oxime esters OXE-03 (produced by BASF) were used.
< coupling agent >
As the silane coupling agent, KBM-503 (produced by Xinyue chemical Co., ltd.) was used.
< leveling agent >
The leveling agent used was a self-made A1, A2, A3 silicone leveling agent, while 3775M (manufactured by Dow Chemical Company) was used as a control.
Examples 4-9 and comparative examples 1-2
The black matrix photosensitive resin compositions of examples 4 to 9 and the compositions of comparative examples 1 to 2 were prepared in the formulations described in table 1.
Table 1 formulation table
Figure BDA0004065775200000181
Figure BDA0004065775200000191
Preparation of light-shielding film
The photosensitive resin composition shown in Table 1 was dropped onto a glass substrate having a surface of 7 cm. Times.7 cm which was dry and clean, and applied by a spin coater to form a coating film having a film thickness of 1.2. Mu.m after the hardening treatment, and left at 23℃for 10 minutes, and then baked for 2 minutes using a heating plate at 120 ℃. Then, the exposure was performed to adjust the exposure gap to 75 μm, and the i-line illuminance was 40mW/cm 2 Is provided with 40mJ/cm exposure 2 The light-shielding film is formed by performing a photo-hardening reaction by ultraviolet irradiation. Then, the light-shielding film was developed with a developing solution of 23℃and 0.022% potassium hydroxide solution under a shower pressure of 0.1MPa for 75sec, and after completion, the light-shielding film was washed with a mist water of 0.15MPa for 10sec to remove the light-shielding filmUnexposed portions of the light film. After development, the black matrix photosensitive resin compositions of examples 4 to 9 and comparative examples 1 to 2 were prepared by post-baking at 230℃for 25 minutes using a hot air dryer.
The black matrix photosensitive resin compositions of examples 4 to 9 and comparative examples 1 to 2 obtained above and the light shielding films formed by curing the same were evaluated as follows.
< surface tension >
The surface tension of the black matrix photosensitive resin compositions of examples 4 to 9 and comparative examples 1 to 2 was measured by a surface tension tester, and the test results are shown in table 2.
< contact Angle >
The contact angles of the black matrix photosensitive resin compositions of examples 4 to 9 and comparative examples 1 to 2 with the glass substrate were measured using a HARKE CAST-KR contact angle tester, and the test results are shown in Table 2.
Example 6 contact angle test chart is shown in fig. 4, example 7 contact angle test chart is shown in fig. 5, comparative example 1 contact angle test chart is shown in fig. 6, and comparative example 2 contact angle test chart is shown in fig. 7.
< surface roughness >
The surface roughness of the light-shielding films formed by curing the black matrix photosensitive resin compositions of examples 4 to 9 and comparative examples 1 to 2 was measured using a Dektak XT roughness tester, test method: x, Y Scan size:10 μm, scan rate:1.0Hz, and the test results are shown in Table 2.
< film thickness uniformity >
The film thickness uniformity of the light-shielding films formed by curing the black matrix photosensitive resin compositions of examples 4 to 9 and comparative examples 1 to 2 was measured by a Dektak XT film thickness tester, three points were measured at fixed positions, the range of the three points was determined, and the calculation results are shown in table 2. The light shielding film is required to have a uniform film thickness to ensure uniform light shielding, and the film thickness should not be extremely large than 0.05 μm.
Table 2 test results
Figure BDA0004065775200000201
From the above test results, the black matrix photosensitive resin compositions of example 4, example 6, and example 8 were lower in surface tension, small in contact angle, strong in spreadability on the surface of the glass substrate, and good in coatability, as compared with the black matrix photosensitive resin composition of comparative example 1, with example 6 being the lowest. The black matrix photosensitive resin compositions of example 5, example 7, and example 9 have smaller surface tension and contact angle, and have strong spreadability on the surface of the glass substrate and good coatability, as compared with the black matrix photosensitive resin composition of comparative example 2, with example 7 being the lowest.
From the above, it is considered that the organosilicon leveling agent provided by the application can effectively reduce the surface tension and enhance the coatability. Good coating properties can still be provided at high carbon black concentrations.
On the other hand, for the light-shielding films, the light-shielding films formed by curing the black matrix photosensitive resin compositions of examples 4 to 9 were lower in surface roughness and better in film thickness uniformity than those formed by curing the black matrix photosensitive resin compositions of comparative examples 1 to 2.
From the above, it can be considered that the organosilicon leveling agent provided by the application forms weak crosslinking in the exposure process due to the unsaturated double bond, the leveling agent is not washed off in the development process, and the post-baking process can also provide a leveling effect, so that the problems of rough surface and uneven film thickness are effectively solved.
From the above, the black matrix photosensitive resin composition provided by the present invention can provide a black matrix having a smooth surface and excellent film thickness uniformity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. An organosilicon leveling agent is characterized by having a structural general formula:
Figure FDA0004065775190000011
wherein a is any integer from 4 to 30, b is any integer from 0 to 10, m is any integer from 4 to 20, n is any integer from 2 to 10, and p is any integer from 4 to 20.
2. The organosilicon leveling agent according to claim 1, wherein m is any integer from 4 to 10, n is any integer from 2 to 6, and p is any integer from 4 to 10;
preferably, m: n: p=4: 2:4 or m: n: p=8: 4:8.
3. a method for preparing the organosilicon leveling agent according to claim 1 or 2, comprising:
the method comprises the steps of (1) carrying out a first reaction on siloxane compounds and benzofuran cyclopropene grease in the presence of a catalyst and a polymerization inhibitor, and adding propenyl polyether compounds to carry out a second reaction after finishing the first reaction;
and after the second reaction is finished, regulating the pH value of the system to hydrolyze the silicon ether to obtain silanol, and then dropwise adding acryloyl chloride to perform a third reaction to obtain the organosilicon leveling agent.
4. The method of claim 3, wherein the siloxane-based compound comprises siloxane C 20 H 65 O 13 Si 12 And/or siloxane C 34 H 113 O 23 Si 22 ；
Preferably, the propenyl polyether compound comprises propenyl polyether C 49 H 98 O 21 ；
Preferably, the catalyst comprises chloroplatinic acid;
preferably, the polymerization inhibitor comprises hydroquinone.
5. A black matrix photosensitive resin composition comprising the silicone leveling agent according to claim 1 or 2;
preferably, the silicone leveling agent is used in an amount of 0.01wt% to 1wt%, preferably 0.01wt% to 0.2wt% of the total solid content mass of the black matrix photosensitive resin composition.
6. The black matrix photosensitive resin composition according to claim 5, further comprising an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, a colorant, and a solvent;
preferably, the black matrix photosensitive resin composition further comprises a curing accelerator, a coupling agent, an antioxidant, a polymerization inhibitor, a defoaming agent; the coupling agent is preferably a silane coupling agent.
7. The black matrix photosensitive resin composition according to claim 6, wherein the alkali-soluble resin is used in an amount of 10 to 30% by weight based on the mass of the entire solid content of the black matrix photosensitive resin composition;
preferably, the alkali-soluble resin includes a resin having a hydroxyl group, a carboxyl group, a phosphate group, a sulfonate group, preferably a carboxyl group, more preferably both an ethylenically unsaturated group and a carboxyl group;
preferably, the alkali-soluble resin comprises a fluorene-based resin, preferably a bisphenol fluorene-based resin;
preferably, the bisphenol fluorene resin is one or more of unsaturated group-containing photosensitive resins obtained by reacting a reactant of an epoxy compound derived from bisphenol fluorene and having two glycidyl ether groups with (meth) acrylic acid with a polycarboxylic acid or an anhydride thereof;
preferably, the bisphenol fluorene derivative epoxy compound with two glycidyl ether groups has a structural general formula:
Figure FDA0004065775190000031
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 Each independently is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and x and y are each independently 0 or 1;
preferably, the bisphenol fluorene-derived epoxy compound with two glycidyl ether groups is obtained by etherification reaction of bisphenol compound and haloalkoxy compound;
preferably, the bisphenol compound includes bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3, 5-dimethylphenyl) ketone, bis (4-hydroxy-3, 5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dimethylphenyl) hexafluoropropane, bis (4-hydroxy-3, 5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dimethylphenyl) dimethylsilane, bis (4-hydroxy-3, 5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3, 5-dichlorophenyl) methane, bis (4-hydroxy-3, 5-dibromophenyl) methane, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxy-3, 5-dimethylphenyl) propane, 2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 2-bis (4-hydroxyphenyl) propane, 2-hydroxy-2-chlorophenyl) propane, 2-bis (4-hydroxyphenyl) ether, 2-hydroxy-2-chlorophenyl) ether, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3, 5-dichlorophenyl) ether, 9-bis (4-hydroxyphenyl) fluorene, 9-bis (4-hydroxy-3-methylphenyl) fluorene, 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9-bis (4-hydroxy-3-bromophenyl) fluorene, 9-bis (4-hydroxy-3-fluorophenyl) fluorene one or more of 9, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dimethylphenyl) fluorene, 9-bis (4-hydroxy-3, 5-dichlorophenyl) fluorene, 9-bis (4-hydroxy-3, 5-dibromophenyl) fluorene, 4 '-biphenol, 3' -biphenol; bisphenol compounds having fluorene-9, 9-diyl are preferred;
preferably, the polycarboxylic acid or anhydride thereof comprises succinic acid, acetyl succinic acid, maleic acid, adipic acid, iconic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, side-oxoglutarate, pimelic acid, sebacic acid, suberic acid, diglycolic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, hexahydrophthalic acid, tetrahydrophthalic acid, norbornanedicarboxylic acid, or monoanhydride thereof;
preferably, the bisphenol fluorene resin has an average molecular weight M w 4000-20000, acid value of 30-200 mgKOH/g; more preferably, the bisphenol fluorene resin has an average molecular weight M w 4000-8000, and an acid value of 30-100 mgKOH/g.
8. The black matrix photosensitive resin composition according to claim 6, wherein the amount of the photopolymerizable monomer is 5% to 25% by weight based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the photopolymerization monomer is selected from one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, polydipentaerythritol pentaacrylate, polydipentaerythritol hexaacrylate and ethylene oxide modified dipentaerythritol hexaacrylate; preferably polydipentaerythritol hexaacrylate;
preferably, the photoinitiator is used in an amount of 0.5wt% to 5wt% based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the photoinitiator is selected from one or more of benzoin derivatives, benzil derivatives, dialkoxyacetophenones, alpha-hydroxyalkyl phenones, alpha-aminoalkylphenones, acyl phosphine oxides, oxime esters, benzoyl formate, benzophenone, thioxanthone, camphorquinone; oxime ester compounds are preferred;
preferably, the colorant is used in an amount of 30wt% to 60wt% based on the total solid content mass of the black matrix photosensitive resin composition;
preferably, the black matrix photosensitive resin composition is cured to form a photoresist film having an optical density of not less than 3.8 in a film thickness of 1 μm;
preferably, the colorant is a carbon black pigment, and is obtained by mixing and grinding raw materials including carbon black, a dispersing agent, a dispersing resin and a solvent, and then adding the solvent for dilution;
preferably, the solvent is used in an amount of 60wt% to 85wt% based on the total mass of the black matrix photosensitive resin composition;
preferably, the solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethyl ethoxypropionate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, propylene glycol diacetate; propylene glycol methyl ether acetate is preferred.
9. A color filter, comprising the black matrix photosensitive resin composition according to any one of claims 5 to 8 as a raw material.
10. A liquid crystal display device comprising the color filter of claim 9.
CN202310074713.1A 2023-01-16 2023-01-16 Organosilicon leveling agent, preparation method thereof, black matrix photosensitive resin composition, color filter and liquid crystal display device Pending CN116144029A (en)

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