WO2014161251A1 - 碱可溶树脂及其制备方法、含有其的光刻胶组合物 - Google Patents

碱可溶树脂及其制备方法、含有其的光刻胶组合物 Download PDF

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Publication number
WO2014161251A1
WO2014161251A1 PCT/CN2013/080171 CN2013080171W WO2014161251A1 WO 2014161251 A1 WO2014161251 A1 WO 2014161251A1 CN 2013080171 W CN2013080171 W CN 2013080171W WO 2014161251 A1 WO2014161251 A1 WO 2014161251A1
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Prior art keywords
alkali
soluble resin
acid
polyether chain
photoresist composition
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PCT/CN2013/080171
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English (en)
French (fr)
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王雪岚
唐琛
常珊
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京东方科技集团股份有限公司
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Priority to US14/239,552 priority Critical patent/US9279037B2/en
Publication of WO2014161251A1 publication Critical patent/WO2014161251A1/zh

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    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • 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
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate

Definitions

  • Embodiments of the present invention relate to an alkali-soluble resin, a method of producing the same, and a photoresist composition containing the same. Background technique
  • the color filter is mainly composed of a substrate, a black matrix, a color film layer, a protective layer, and a conductive layer.
  • the colored photoresist composition is applied to a substrate to form a photoresist layer, and the photoresist layer is exposed to form a predetermined photoresist pattern, and the photoresist pattern is developed and post-baked to obtain a color film layer. .
  • the slope angle of the film layer is primarily dependent on the film forming properties of the photoresist composition.
  • the main components of the general photoresist composition include alkali-soluble resins, photoactive compounds, photoinitiators, pigment dispersions, organic solvents, and other additives.
  • the photoactive compound will form a polymer after exposure and high temperature, and some polymers have high hardness and are not easy to bend and form a slope, resulting in a large gradient of the film layer, so the connection between the color film layer and the black matrix is prone to voids.
  • the slope angle is too large to affect the coating and rubbing effect of the alignment layer in the liquid crystal glass cell in the subsequent process, and may also cause light leakage; it may even affect the liquid crystal orientation, thereby affecting the display quality of the picture.
  • Keeping the slope angle of the color film layer in an appropriate range (23° - 60°) is the focus of development of the photoresist composition. Summary of the invention
  • An embodiment of the present invention provides an alkali-soluble resin, wherein the alkali-soluble resin is a polyether chain-containing acrylic acid-soluble solvent obtained by grafting an alkali-soluble resin with a polyether chain-containing monobasic acid. Resin.
  • the monobasic acid structure is as follows:
  • the acryl-based soluble resin may include any one of a methacrylate, an amine-modified acrylate, a polycyclic aromatic aryl alkali-soluble resin, and a hyperbranched alkali-soluble acrylated polyester.
  • the alkali-soluble resin contains less than 100 carbon atoms.
  • the embodiment of the present invention further provides a method for preparing an alkali soluble resin, which comprises the following steps: 1) adipic acid, 1,3-dibromo-5,5-dimethylhydantoin in a solvent dichloromethane The reaction is carried out to obtain 1-bromohexanoic acid; 1-bromohexanoic acid is reacted with sodium hydroxide to obtain sodium 1-hydroxyhexanoate; sodium 1-hydroxyhexanoate is reacted with acryloyl chloride to obtain an adipic acid activating substance;
  • the ratio of the parts by weight of the polyethylene glycol and the adipic acid activator in the step 2 ranges from 1:0.5 to 1:0.95.
  • the ratio of the parts by weight of the polyether chain-containing monobasic acid and the alkali-soluble resin in the step 3 is 1:0.45 to 1:0.83.
  • Embodiments of the present invention also provide a photoresist composition comprising the above-described alkali-soluble resin.
  • the photoresist composition may include the following components by weight: alkali soluble resin: 7%-24%;
  • Photoactive compound 10%-22%
  • the photoinitiator may include one or more of a benzoin substance, a benzophenone substance, and an anthraquinone substance.
  • the photoactive compound may include one or more of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, and ethoxylated pentaerythritol tetraacrylate.
  • the photoresist composition may further include a solvent component including propylenedione methyl ether acetate, propylene glycol diacetate, and ethyl 3-ethoxy-3-imidopropionate.
  • a solvent component including propylenedione methyl ether acetate, propylene glycol diacetate, and ethyl 3-ethoxy-3-imidopropionate.
  • 2-heptane, 3-heptane, cyclopentanone, and cyclohexanone One or more of 2-heptane, 3-heptane, cyclopentanone, and cyclohexanone.
  • Figure 1 is a flow chart showing the preparation process of an alkali-soluble resin in Example 1 of the present invention.
  • Figure 2 is a structural view showing a grafted polyether chain in Example 1 of the present invention.
  • Fig. 3 is a schematic view showing the slope angle of the color film layer prepared in Example 1 of the present invention.
  • Fig. 4 is a view showing the slope angle of the color film layer prepared in Example 2 of the present invention.
  • Fig. 5 is a view showing the slope angle of the color film layer prepared in Example 3 of the present invention.
  • Fig. 6 is a view showing the slope angle of the color film layer prepared in Example 4 of the present invention.
  • Figure 7 is a schematic illustration of the slope angle of a color film layer prepared in accordance with a comparative example of the present invention. Detailed ways
  • An embodiment of the present invention provides an alkali-soluble resin, which is a polyether chain-containing acrylic acid-soluble solvent obtained by grafting an alkali-soluble resin with an acrylic acid-containing resin. Resin.
  • polyether chain-containing monobasic acid For example, the structural formula of the polyether chain-containing monobasic acid is as follows:
  • n is an integer in the range 7-30.
  • the acryl-based soluble resin may include any one of a methacrylate, an amine-modified acrylate, a polycyclic aromatic aryl alkali-soluble resin, and a hyperbranched alkali-soluble acrylated polyester.
  • the alkali-soluble resin contains less than 100 carbon atoms.
  • the polyether-linked branched acrylic acid-soluble resin of the embodiment of the present invention is added to the photoresist combination
  • the alkali-soluble resin since the alkali-soluble resin has a double bond, it can participate in the polymerization reaction upon exposure and post-baking, so that a denser flexible network can be formed, and at the same time, it is still soft after baking after high temperature. Since the internal rotation barrier of the ether bond in the alkali-soluble resin is small and the dynamic flexibility is good, under gravity, it is easy to cause other components of the photoresist to bend and sink naturally, thereby forming a small slope. .
  • the color film layer prepared from the photoresist composition containing the alkali-soluble resin has a small slope angle and can be controlled at 25 to 55. Within the range, the phenomenon that the connection between the color film layer and the black matrix is prone to voids and light leakage is avoided.
  • the photoresist composition of the embodiment of the invention improves the coating and rubbing effect of the alignment layer in the liquid crystal glass cell in the subsequent process, improves the liquid crystal orientation, and thereby improves the display T quality of the picture.
  • the embodiment of the present invention also provides a method for preparing the above alkali-soluble resin, which comprises the following steps:
  • Adipic acid 1,3-dibromo-5,5-dimethylhydantoin is reacted in a solvent of dichloromethane to obtain 1-bromohexanoic acid; 1-bromohexanoic acid is reacted with sodium hydroxide to obtain 1-hydroxyl group Sodium hexate; reacting sodium 1-hydroxyhexanoate with acryloyl chloride to obtain adipic acid activator;
  • the polyethylene glycol and the adipic acid activator are reacted in a solvent hydrazine, hydrazine-dimethylformamide to obtain a polybasic acid containing a polyether chain;
  • the polyether chain-containing monobasic acid and the acrylic acid alkali soluble resin are reacted in a solvent hydrazine, hydrazine-dimethylformamide to obtain a polyether chain-containing acrylic alkali-soluble resin.
  • the ratio of the parts by weight of the polyethylene glycol and the adipic acid activator in the step 2 ranges from 1:0.5 to 1:0.95.
  • the ratio of the parts by weight of the polyether chain-containing monobasic acid and the acrylic acid alkali soluble resin in the step 3 is in the range of 1:0.45 to 1:0.83.
  • Embodiments of the present invention also provide a photoresist composition comprising the above alkali-soluble resin.
  • the photoresist composition comprises the following weight percentage components:
  • Alkali soluble resin 7%-24%
  • Photoactive compound 10%-22%
  • Photoinitiator 1.3%-12.5%.
  • Any photoactive compound that can be used for this purpose can include double seasons One or more of pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate.
  • Photoinitiators suitable for use in embodiments of the invention may be any photoinitiator known to those skilled in the art for this purpose.
  • the photoinitiator may include one or more of a benzoin substance, a benzophenone substance, an anthraquinone substance.
  • the photoresist composition may also include a solvent component.
  • the solvent is not particularly limited as long as it can dissolve or disperse the components of the photoresist composition, does not react with the above components, and has a certain volatility.
  • the solvent may be propylene glycol methyl ether acetate, propylene glycol diacetate, ethyl 3-ethoxy-3-imide propionate, 2-heptane, 3-heptane, cyclopentanone, cyclohexane One or more of the ketones.
  • the solvent may be present in an amount from 3% to 21% by weight of the photoresist composition.
  • pigment dispersions such as pigment dispersions, other additives such as coupling agents, antioxidants, ultraviolet diluents or crosslinking agents.
  • additives such as coupling agents, antioxidants, ultraviolet diluents or crosslinking agents.
  • the pigment dispersion may be present in an amount from about 40% to about 70% by weight of the photoresist composition, such as from about 48% to about 69%.
  • the additive may be present in an amount from about 0.05% to about 1.5% by weight of the photoresist composition, such as from about 0.07% to about 1.0%.
  • a photoresist composition containing the alkali-soluble resin includes the following components by weight: alkali-soluble resin: 7% to 24%;
  • Photoactive compound 10%-22%
  • Additives may be added as needed, such as: coupling agents, antioxidants, UV absorbers, crosslinkers, leveling agents or other auxiliaries, etc., not listed here.
  • Example 1 The present embodiment provides an alkali soluble resin, a preparation method thereof, and a photoresist composition containing the alkali soluble resin.
  • the preparation method of the alkali soluble resin is as follows (the preparation process is shown in Figure 1):
  • the NMR data of the adipic acid activator are as follows: NMR (300 MHz, CDC1 3 , ppm) ⁇ : 2.11-2.72 (m, 6H), 3.82 (s, lH), 4.06 (s, lH), 4.89 (s , 2H), 5.3 ( s, lH ) , 11.8 ( s, 2H ).
  • Polyethylene glycol 400, adipic acid activator, hydrazine, dimethyl-dimethylformamide (DMF) as a solvent were added to a round bottom flask (the weight ratio of the three is shown in Table 1), at 80 ° C Reflux for 6 h. After the reaction was stopped, the DMF solvent was removed by steaming under reduced pressure. It was added dropwise to 30 parts by weight of acetone, and washed three times by the above method to obtain a white solid, which was dried in vacuo to give a polyether chain-containing monobasic acid, wherein the structural formula of the polyether chain is shown in Fig. 2.
  • the hyperbranched alkali-soluble acrylated polyester used in this example has a structure represented by the following formula (I):
  • R 2 is methyl, ethyl, phenyl, tea, polycyclic aryl, methylamino, hydrazine; hydrogen or methyl;
  • m, q, p All are integers in the range of 9-15;
  • a and b are integers in the range of 1-5.
  • the polyether chain-containing monobasic acid, the hyperbranched alkali-soluble acrylated polyester (1) prepared in 1.2), the hydrazine, hydrazine-dimethylformamide (DMF) as a solvent are added to the round bottom flask ( The weight ratio of the three is shown in Table 1), and an appropriate amount of concentrated sulfuric acid was added as a catalyst, and refluxed at 135 ° C for 12 h. After the reaction was stopped and cooled, the DMF solvent was removed by steaming under reduced pressure. It is added dropwise to 50 parts by weight of cyclohexanone, washed three times by the above method, and dried under vacuum to obtain a white solid, that is, an alkali-soluble resin.
  • the structural formula ( ⁇ ) is shown in Fig. 1, wherein, it is a methyl group or an ethyl group; 2 is any one of a methyl group, an ethyl group, a phenyl group, a tea group, a polycyclic aryl group, a methylamino group, and a biphenyl group; R 3 is hydrogen or a methyl group; and m, q, and p are all in the range of 9-15.
  • An integer; a, b are integers in the range of 1-5.
  • a photoresist composition was prepared according to the components and contents listed in Table 1. The components were thoroughly stirred to form a photoresist composition, which was applied to a glass substrate having a black matrix, labeled as Sample 1, and having a thickness of 2.6 ⁇ m. Baking in an oven at 80-110 ° C for 3 min, exposing with ultraviolet light with an illuminance of 125 mJ/cm 2 , developing in a developing solution at room temperature for 30 s, washing with deionized water, and drying, at 230 ° Bake at 45 ° C for 45 min.
  • Example 2 The glass was sliced, sampled, and the cross section was examined by scanning electron microscopy (SEM) to observe the slope. The results are shown in Figure 3, where the slope angle is 28.3°. It can be seen that the film layer has a small slope angle and can effectively avoid light leakage.
  • SEM scanning electron microscopy
  • the present embodiment provides an alkali soluble resin, a preparation method thereof, and a photoresist containing the alkali soluble resin combination.
  • the preparation method of the alkali soluble resin is as follows:
  • the preparation method of the adipic acid activator is the same as the preparation method of the adipic acid activator in Example 1. 2.2) Preparation of monobasic acid containing polyether chain
  • a photoresist composition was prepared according to the components and contents listed in Table 1. The components were thoroughly stirred to form a photoresist composition, which was applied to a glass substrate having a black matrix, labeled as Sample 2, and having a thickness of 2.6 ⁇ m. Baking in an oven at 80-110 ° C for 3 min, exposing with ultraviolet light with an illuminance of 125 mJ/cm 2 , developing in a developing solution at room temperature for 30 s, washing with deionized water, and drying, at 230 ° Bake at 45 ° C for 45 min.
  • Example 3 The glass was sliced, sampled, and examined by scanning electron microscopy (SEM) to observe the cross section and observe the slope. The results are shown in Figure 4, where the slope angle is 39.5°. It can be seen that the film layer has a small slope angle and can effectively avoid light leakage.
  • SEM scanning electron microscopy
  • the present embodiment provides an alkali-soluble resin, a preparation method thereof, and a photoresist composition containing the alkali-soluble resin.
  • the preparation method of the alkali soluble resin is as follows:
  • Polyethylene glycol 1200, adipic acid activator, hydrazine, dimethyl-dimethylformamide (DMF) as a solvent were added to a round bottom flask (the weight ratio of the three is shown in Table 1), at 100 ° C Reflux for 6-10h. After the reaction was stopped, the DMF solvent was distilled off under reduced pressure. It was added dropwise to 70 parts by weight of acetone, and washed three times by the above method to obtain a white solid, which was dried in vacuo to give a polyether chain-containing monobasic acid, wherein the structural formula of the polyether chain is shown in Fig. 2.
  • a photoresist composition was prepared according to the components and contents listed in Table 1. The components were thoroughly stirred to form a photoresist composition, which was applied to a glass substrate having a black matrix, labeled as Sample 3, and having a thickness of 2.6 ⁇ m. Baking in an oven at 80-110 ° C for 3 min, exposing with ultraviolet light with an illuminance of 125 mJ/cm 2 , developing in a developing solution at room temperature for 30 s, washing with deionized water, and drying, at 230 ° Bake at 45 ° C for 45 min.
  • Example 4 The glass was sliced, sampled, and examined by scanning electron microscopy (SEM) to observe the cross section and observe the slope. The results are shown in Figure 5, where the slope angle is 51.7°. It can be seen that the film layer has a small slope angle and can effectively avoid light leakage.
  • SEM scanning electron microscopy
  • the present embodiment provides an alkali-soluble resin, a preparation method thereof, and a photoresist composition containing the alkali-soluble resin.
  • the preparation method of the alkali soluble resin is as follows:
  • the preparation method of the adipic acid activator is the same as the preparation method of the adipic acid activator in Example 1.
  • the polyether chain-containing monobasic acid, methacrylate, and hydrazine, dimethyl-dimethylformamide (DMF) as a solvent were added to a round bottom flask (the weight ratio of the three is shown in Table 1).
  • the DMF solvent was distilled off under reduced pressure.
  • 80 parts by weight of cyclohexanone was added dropwise, washed three times by the above method, and dried under vacuum to give a white solid, that is, an alkali-soluble resin.
  • a photoresist composition was prepared according to the components and contents listed in Table 1. The components were thoroughly stirred to form a photoresist composition, which was applied to a glass substrate having a black matrix, labeled as Sample 4, and having a thickness of 2.6 ⁇ m. Bake in an oven at 80-110 ° C for 3 min, expose to ultraviolet light with an illuminance of 125 mJ/cm 2 , and then develop in a developing solution at room temperature for 30 s, rinse with deionized water, and blow dry at 230 ° C. Bake for 45 min under temperature conditions.
  • the glass was sliced, sampled, and examined by scanning electron microscopy (SEM) to observe the cross section and observe the slope. Obtain the slope angle of the film as shown in Fig. 7, where the slope angle is 45.0°. It can be seen that the slope angle of the film layer is small, and light leakage can be effectively avoided. Comparative example
  • the alkali-soluble resin in the photoresist composition of Example 4 was replaced with an equivalent weight percentage of an alkali-soluble resin, and the other components and contents were the same as in Example 4 to prepare a photoresist composition.
  • the other steps were the same as in Example 4, and the slope angle of the film layer was obtained as shown in Fig. 7, wherein the slope angle was 76.0. It can be seen that the film layer has a large slope angle and is easy to leak light.
  • Each reactant contains a polyether chain of monobasic acid:
  • the acrylic acid used in the examples can be reduced to a high-branched alkali-soluble amine-modified epoxy aromatic acid methyl methacrylate type acrylated acrylate acrylate half ester ester polyester

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Abstract

一种碱可溶树脂及其制备方法、含该树脂的光刻胶组合物。该碱可溶树脂为含聚醚链的丙烯酸碱可溶树脂。包括该碱可溶树脂的光刻胶组合物，可使膜层的坡度角降低，避免了彩色膜层和黑矩阵之间连接容易出现空隙而造成的漏光现象，可改善取向层的涂覆及摩擦效果。

Description

碱可溶树脂及其制备方法、 含有其的光刻胶组合物 技术领域
本发明的实施例涉及一种碱可溶树脂及其制备方法、含该树脂的光刻胶 组合物。 背景技术
彩色滤光片主要由基板、 黑矩阵、 彩色膜层、 保护层和导电层组成。 一 般采用将着色的光刻胶组合物应用到基板上形成光刻胶层， 将光刻胶层曝光 后形成预定的光刻胶图案， 对光刻胶图案进行显影和后烘， 获得彩色膜层。
在彩色滤光片中， 对上述膜层的坡度角有一定的要求， 坡度角太大， 很 容易造成漏光。 膜层的坡度角主要取决于光刻胶组合物的成膜性质。 一般光 刻胶组合物的主要成分包括碱可溶树脂、 光活性化合物、 光引发剂、 颜料分 散液、 有机溶剂以及其它添加剂。 光活性化合物在曝光和高温后烘会形成聚 合物，有些聚合物硬度较大， 不易弯折下陷形成坡度，导致膜层坡度角 艮大， 因此彩色膜层和黑矩阵之间的连接容易出现空隙，从而造成漏光现象； 另夕卜， 坡度角太大影响后续工艺中液晶玻盒中取向层的涂覆及摩擦效果， 也可能造 成漏光； 甚至也会影响液晶取向， 从而影响画面的显示品质。 使彩色膜层的 坡度角保持在适当的范围 （23° -60° )成为光刻胶组合物研发的重点。 发明内容
本发明的实施例提供一种碱可溶树脂， 所述的碱可溶树脂为通过丙烯酸 碱可溶树脂与含聚醚链的一元酸接枝而制得的含聚醚链的丙烯酸碱可溶树 脂。
例如， 一元酸结构式如下：
Figure imgf000002_0001
其中： n为 7-30范围内的整数。 例如，所述的丙烯酸碱可溶树脂可包括甲基丙烯酸酯、胺改性丙烯酸酯、 多环芳侧基丙烯酸碱可溶树脂、 高支化碱溶型丙烯酸化聚酯中的任意一种。
例如， 所述的碱可溶树脂含有的碳原子数小于 100。
本发明的实施例还提供一种碱可溶树脂的制备方法， 其包括如下步骤： 1 )将己二酸、 1,3-二溴 -5,5-二甲基海因在溶剂二氯甲烷中反应获得 1- 溴己酸； 将 1-溴己酸与氢氧化钠反应获得 1-羟基己酸钠； 将 1-羟基己酸钠 与丙烯酰氯反应获得己二酸活化物；
2 )将聚乙二醇和己二酸活化物在溶剂 Ν,Ν-二甲基甲酰胺中进行反应获 得含聚醚链的一元酸；
3 )将含聚醚链的一元酸和丙烯酸碱可溶树脂在溶剂 Ν,Ν-二甲基甲酰胺 中进行反应获得含聚醚链的丙烯酸碱可溶树脂。
例如， 步骤 2中聚乙二醇、 己二酸活化物的重量份数之比的范围为 1： 0.5至 1： 0.95。
例如， 步骤 3中含聚醚链的一元酸、 丙烯酸碱可溶树脂的重量份数之比 的范围为 1： 0.45至 1： 0.83。
本发明的实施例还提供一种光刻胶组合物，所述的光刻胶组合物包括上 述的碱可溶树脂。
例如， 所述的光刻胶组合物， 可以包括以下重量百分比的组分： 碱可溶树脂： 7%-24%；
光活性化合物： 10%-22%；
光致引发剂： 1.3%-12.5%„
例如， 所述的光致引发剂可以包括安息香类物质、二苯甲酮类物质、 蒽 醌类物质的一种或几种。
例如，所述的光活性化合物可以包括双季戊四醇五丙烯酸酯、双季戊四 醇六丙烯酸酯、异戊四醇四丙烯酸酯、 乙氧化异戊四醇四丙烯酸酯中的一种 或几种。
例如，所述的光刻胶组合物还可以包括溶剂组分，所述的溶剂包括丙二 酮甲醚醋酸酯、 丙二醇二乙酸酯、 3-乙氧基 -3-亚胺丙酸乙酯、 2-庚烷、 3-庚 烷、 环戊酮、 环己酮中的一种或几种。 附图说明 为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实 施例或现有技术描述中所需要使用的附图作筒单地介绍，显而易见地，下面 描述中的附图仅仅是本发明的一些实施例， 对于本领域普通技术人员来讲， 在不付出创造性劳动性的前提下， 还可以根据这些附图获得其他的附图。
图 1为本发明实施例 1中碱可溶树脂的制备工艺流程图。
图 2为本发明实施例 1中接枝的聚醚链的结构图。
图 3为本发明实施例 1所制备的彩色膜层的坡度角的示意图。
图 4为本发明实施例 2所制备的彩色膜层的坡度角的示意图。
图 5为本发明实施例 3所制备的彩色膜层的坡度角的示意图。
图 6为本发明实施例 4所制备的彩色膜层的坡度角的示意图。
图 7为本发明对比例所制备的彩色膜层的坡度角的示意图。 具体实施方式
为使本领域技术人员更好地理解本发明的技术方案，下面结合附图和具 体实施方式对本发明作进一步详细描述。 显然， 所描述的实施例仅仅是 本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例， 本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其 他实施例， 都属于本发明保护的范围。
本发明的实施例提供一种碱可溶树脂，所述的碱可溶树脂为通过丙烯酸 碱可溶树脂与含聚醚链的一元酸接枝而制得的含聚醚链的丙烯酸碱可溶树 脂。
例如， 所述含聚醚链的一元酸结构式如下：
Figure imgf000004_0001
其中： n为 7-30范围内的整数。
例如，所述的丙烯酸碱可溶树脂可包括甲基丙烯酸酯、胺改性丙烯酸酯、 多环芳侧基丙烯酸碱可溶树脂、 高支化碱溶型丙烯酸化聚酯中的任意一种。 所述的碱可溶树脂含有的碳原子数小于 100。
当本发明实施例的聚醚链接枝的丙烯酸碱可溶树脂加入到光刻胶组合 物中时， 由于该碱可溶树脂带有双键， 其在曝光和后烘时可参与聚合反应， 从而可形成更加致密的柔性网络， 同时， 在高温后烘后依然柔软。 由于该碱 可溶树脂中的醚键的内旋转位垒较小， 动态柔性好， 因此在重力作用下， 其 容易带动光刻胶的其他成分弯折下陷并自然流动，从而形成较小的坡度。 由 含所述碱可溶树脂的光刻胶组合物制备的彩色膜层的坡度角较小，可控制在 25° -55。 范围内， 从而避免了彩色膜层和黑矩阵之间的连接容易出现空隙 而造成漏光的现象。此外，本发明实施例的光刻胶组合物改善了后续工艺中 液晶玻盒中取向层的涂覆及摩擦效果， 改善了液晶取向，从而提高了画面的 显 T 品质。
本发明的实施例还提供了上述碱可溶树脂的制备方法， 其包括如下步 骤：
1 ) 己二酸活化物的制备
将己二酸、 1,3-二溴 -5,5-二甲基海因在溶剂二氯甲烷中反应获得 1-溴己 酸； 将 1-溴己酸与氢氧化钠反应获得 1-羟基己酸钠； 将 1-羟基己酸钠与丙 烯酰氯反应获得己二酸活化物；
2 )含聚醚链的一元酸的制备
将聚乙二醇和己二酸活化物在溶剂 Ν,Ν-二甲基甲酰胺中进行反应获得 含聚醚链的一元酸；
3 )含聚醚链的丙烯酸碱可溶树脂的制备
将含聚醚链的一元酸和丙烯酸碱可溶树脂在溶剂 Ν,Ν-二甲基甲酰胺中 进行反应获得含聚醚链的丙烯酸碱可溶树脂。
步骤 2中聚乙二醇、己二酸活化物的重量份数之比的范围为 1： 0.5至 1 : 0.95。 步骤 3中含聚醚链的一元酸、 丙烯酸碱可溶树脂的重量份数之比的 范围为 1： 0.45至 1： 0.83。
本发明的实施例还提供一种包含上述碱可溶树脂的光刻胶组合物。 所述的光刻胶组合物， 包括以下重量百分比的组分：
碱可溶树脂： 7%-24%；
光活性化合物： 10%-22%；
光致引发剂： 1.3%-12.5%。 的可用于此目的的任何光活性化合物。例如，所述光活性化合物可包括双季 戊四醇五丙烯酸酯、双季戊四醇六丙烯酸酯、异戊四醇四丙烯酸酯、 乙氧化 异戊四醇四丙烯酸酯中的一种或几种。
适合用于本发明实施例中的光致引发剂可以是本领域技术人员已知的 可用于此目的的任何光致引发剂。例如，所述光致引发剂可包括安息香类物 质、 二苯甲酮类物质、 蒽醌类物质的一种或几种。
所述光刻胶组合物还可包括溶剂组分。对溶剂没有特别地限定，只要能 够溶解或分散光刻胶组合物的组分，不与上述组分反应，并有一定的挥发性 即可。 例如， 溶剂可以为丙二酮甲醚醋酸酯、 丙二醇二乙酸酯、 3-乙氧基 -3- 亚胺丙酸乙酯、 2-庚烷、 3-庚烷、 环戊酮、 环己酮中的一种或几种。 溶剂可 以以光刻胶组合物重量的 3%-21%的量存在。 其他任选的组分， 诸如， 颜料分散液， 诸如偶联剂、 抗氧化剂、 紫外稀释剂 或交联剂等的其他添加剂。本领域技术人员在阅读本说明书之后，很容易确 定某种或某些任选的组分及其含量， 以满足特定的应用。 例如，颜料分散液 可以以所述光刻胶组合物重量的约 40%-70%的量存在， 诸如约 48%-69%。 添加剂可以以所述光刻胶组合物重量的约 0.05%-1.5%的量存在， 诸如约 0.07%- 1.0%。
例如， 含该碱可溶树脂的光刻胶组合物， 包括以下重量百分比的组分： 碱可溶树脂： 7%-24%；
光活性化合物： 10%-22%；
光致引发剂： 1.3%-12.5%；
颜料分散液： 48%-69%；
溶剂： 3%-21%；
添加剂： 0.07%- 1.0%。
添加剂可根据需要添加，如： 偶联剂、抗氧化剂、 紫外吸收剂、 交联剂、 流平剂或其它助剂等， 在此不——列举。
为了更好地说明上述碱可溶树脂及其制备方法、 含有其的光刻胶组合 物， 下面以几个具体实施例进行详细说明。应理解， 所述实施例仅仅是说明 性的， 无意限定本发明的范围。 实施例 1 本实施例提供一种碱可溶树脂及其制备方法、含该碱可溶树脂的光刻胶 组合物。
其中碱可溶树脂的制备方法介绍如下 （制备工艺流程见图 1 ):
1.1 ) 己二酸活化物的制备
将 1重量份的己二酸、 0.5重量份的 1,3-二溴 -5,5-二甲基海因、 50重量 份的二氯甲烷（溶剂）加入到 lOOmL圓底烧瓶中， 室温搅拌， 反应 2.5h。 反应结束后， 过滤， 滤液用 40重量份的水洗涤 3次。 合并有机相， 用无水 硫酸钠干燥， 得 1-溴己二酸。
将 1重量份的 1-溴己二酸加入到 2.3重量份的 30%的氢氧化钠溶液中， 加热到 100°C反应 4h。 用 50重量份的二氯甲烷（溶剂）萃取 3次， 有机相 用无水硫酸钠干燥， 得到 1-羟基己二酸钠。
将 1重量份的 1-羟基己二酸钠加入到 2.56份 20%硫酸溶液中， 加热到 100°C反应 3h。 用 50重量份的二氯甲烷（溶剂）萃取 3次， 有机相用无水 硫酸钠干燥， 得到 1-羟基己二酸。
将 2重量份的 1-羟基己二酸和 0.6重量份的丙烯酰氯加入到三口瓶中。 加入适量的四氢呋喃溶剂， 在冰浴下加入适量的三乙胺催化剂， 升温到 70 °C , 在氮气氛下回流过夜。反应完成后减压蒸馏除去溶剂， 并用高压液相 色语做分离， 进一步除去溶剂。 固体用环己烷做重结晶， 过滤， 真空干燥， 得到己二酸活化物。 该己二酸活化物的核磁共振数据如下： NMR (300 MHz, CDC13, ppm) δ: 2.11-2.72 (m, 6H), 3.82(s,lH), 4.06 ( s,lH ) , 4.89 (s, 2H), 5.3 ( s,lH ) , 11.8 ( s,2H )。
1.2 )含聚醚链的一元酸的制备
将聚乙二醇 400、 己二酸活化物、作为溶剂的 Ν,Ν-二甲基甲酰胺 (DMF) 加入到圓底烧瓶中 （三者的重量比见表 1 ), 在 80°C下回流 6h。 停止反应冷 却后， 减压蒸愤除去 DMF溶剂。 逐滴加入 30重量份的丙酮中， 用上述方 法洗涤三次， 得到白色固体， 真空干燥， 得到含聚醚链的一元酸， 其中， 聚 醚链的结构式见图 2。
1.3 )含聚醚链的丙烯酸碱可溶树脂的制备
首先，该实施例中使用的高支化碱溶型丙烯酸化聚酯具有如下式 (I)所示 的结构：
Figure imgf000008_0001
其中， 为甲基或乙基； R2为甲基、 乙基、 苯基、 茶基、 多环芳基、 甲氨基、 联 中的任意一种； 为氢或甲基； m、 q、 p均为 9-15范围内 的整数； a、 b均为 1-5范围内的整数。
将 1.2 ) 中制备的含聚醚链的一元酸、 高支化碱溶型丙烯酸化聚酯 (1)、 作为溶剂的 Ν,Ν-二甲基甲酰胺 (DMF)加入到圓底烧瓶中 （三者的重量比见 表 1 ), 加适量的浓硫酸作催化剂， 135 °C下回流 12h。 停止反应冷却后， 减 压蒸愤除去 DMF溶剂。 逐滴加入 50重量份环己酮中， 用上述方法洗涤 3 次， 真空干燥， 得到白色固体， 即碱可溶树脂， 其结构式（Π )见图 1 , 其 中， 为甲基或乙基； R2为甲基、 乙基、 苯基、 茶基、 多环芳基、 甲氨基、 联氨基中的任意一种； R3为氢或甲基； m、 q、 p均为 9-15范围内的整数； a、 b均为 1-5范围内的整数。
光刻胶组合物的制备
根据表 1所列举的组分和含量制备光刻胶组合物。将所述的组分充分搅 拌， 制成光刻胶组合物， 涂覆于具有黑矩阵的玻璃基板上， 标记为样品 1 , 厚度为 2.6微米。在 80-110°C烘箱中烘烤 3min,用照度为 125mJ/cm2的紫外 光进行曝光处理后，在室温下显影液中显影 30s, 经去离子水洗净后， 吹干， 在 230°C的温度条件下烘烤 45min。
将玻璃切片、 制样， 采用扫描电子显微镜（SEM )测试截面、 观察坡 度。 结果见图 3 , 其中坡度角为 28.3° 。 可见膜层的坡度角较小， 能有效地 避免漏光。 实施例 2
本实施例提供一种碱可溶树脂及其制备方法、含该碱可溶树脂的光刻胶 组合物。
其中碱可溶树脂的制备方法介绍如下：
2.1 ) 己二酸活化物的制备
己二酸活化物的制备方法与实施例 1中己二酸活化物的制备方法相同。 2.2 )含聚醚链的一元酸的制备
将聚乙二醇 800、 己二酸活化物、作为溶剂的 Ν,Ν-二甲基甲酰胺 (DMF) 加入到圓底烧瓶中（三者的重量比见表 1 ), 在 120°C下回流 10 h。停止反应 冷却后， 减压蒸愤除去 DMF溶剂。 逐滴加入 100重量份的丙酮中， 用上述 方法洗涤三次， 得到白色固体， 真空干燥， 得到含聚醚链的一元酸， 其中， 聚醚链的结构式见图 2。
2.3 )含聚醚链的丙烯酸碱可溶树脂的制备
将 2.2 ) 中制备的含聚醚链的一元酸、 胺改性环氧丙烯酸酯（UV1101 , 上海信茂化工贸易有限公司）、 Ν,Ν-二甲基甲酰胺 (DMF)加入到圓底烧瓶中 (三者的重量比见表 1 ), 加适量的浓硫酸作催化剂， 180°C下回流 18 h。 停 止反应冷却后， 减压蒸愤除去 DMF溶剂。 逐滴加入 150重量份环己酮中， 用上述方法洗涤 3次， 真空干燥， 得到白色固体， 即碱可溶树脂。
光刻胶组合物的制备
根据表 1 所列举的组分和含量制备光刻胶组合物。 将所述组分充分搅 拌， 制成光刻胶组合物， 涂覆于具有黑矩阵的玻璃基板上， 标记为样品 2, 厚度为 2.6微米。在 80-110°C烘箱中烘烤 3min,用照度为 125mJ/cm2的紫外 光进行曝光处理后，在室温下显影液中显影 30s, 经去离子水洗净后， 吹干， 在 230°C的温度条件下烘烤 45min。
将玻璃切片、 制样， 扫描电子显微镜（SEM ) 测试截面、 观察坡度。 结果见图 4, 其中坡度角为 39.5° 。 可见膜层的坡度角较小， 能有效地避免 漏光。 实施例 3
本实施例提供一种碱可溶树脂及其制备方法、含该碱可溶树脂的光刻胶 组合物。
其中碱可溶树脂的制备方法介绍如下：
3.1 ) 己二酸活化物的制备 己二酸活化物的制备方法与实施例 1中己二酸活化物的制备方法相同。
3.2 )含聚醚链的一元酸的制备
将聚乙二醇 1200、己二酸活化物、作为溶剂的 Ν,Ν-二甲基甲酰胺 (DMF) 加入到圓底烧瓶中 （三者的重量比见表 1 ), 在 100°C下回流 6-10h。 停止反 应冷却后， 减压蒸馏除去 DMF溶剂。 逐滴加入 70重量份的丙酮中， 用上 述方法洗涤三次，得到白色固体，真空干燥，得到含聚醚链的一元酸，其中， 聚醚链的结构式见图 2。
3.3 )含聚醚链的丙烯酸碱可溶树脂的制备
将 3.2 ) 中制备的含聚醚链的一元酸、 芳香酸甲基丙烯酸半酯（SB401 , 沙多玛（广州 )化学有限公司）、 作为溶剂的 Ν,Ν-二甲基甲酰胺 (DMF)加入 到圓底烧瓶中（三者的重量比见表 1 ), 加适量的浓硫酸作催化剂， 150°C下 回流 15h。 停止反应冷却后， 减压蒸馏除去 DMF溶剂。 逐滴加入 100重量 份环己酮中， 用上述方法洗涤 3次， 真空干燥， 得到白色固体， 即碱可溶树 脂。
光刻胶组合物的制备
根据表 1 所列举的组分和含量制备光刻胶组合物。 将所述组分充分搅 拌， 制成光刻胶组合物， 涂覆于具有黑矩阵的玻璃基板上， 标记为样品 3, 厚度为 2.6微米。在 80-110°C烘箱中烘烤 3min,用照度为 125mJ/cm2的紫外 光进行曝光处理后，在室温下显影液中显影 30s, 经去离子水洗净后， 吹干， 在 230°C的温度条件下烘烤 45min。
将玻璃切片、 制样， 扫描电子显微镜（SEM ) 测试截面、 观察坡度。 结果见图 5, 其中坡度角为 51.7° 。 可见膜层的坡度角较小， 能有效地避免 漏光。 实施例 4
本实施例提供一种碱可溶树脂及其制备方法、含该碱可溶树脂的光刻胶 组合物。
其中碱可溶树脂的制备方法介绍如下：
4.1 ) 己二酸活化物的制备
己二酸活化物的制备方法与实施例 1中己二酸活化物的制备方法相同。
4.2 )含聚醚链的一元酸的制备 将聚乙二醇 400、 己二酸活化物、作为溶剂的 Ν,Ν-二甲基甲酰胺 (DMF) 加入到圓底烧瓶中 （三者的重量比见表 1 ), 在 90°C下回流 7h。 停止反应冷 却后， 减压蒸愤除去 DMF溶剂。 逐滴加入 80重量份的丙酮中， 用上述方 法洗涤三次， 得到白色固体， 真空干燥， 得到含聚醚链的一元酸， 其中， 聚 醚链的结构式见图 2。
4.3 )含聚醚链的丙烯酸碱可溶树脂的制备
将 4.2 )中制备的含聚醚链的一元酸、 甲基丙烯酸酯、 作为溶剂的 Ν,Ν- 二甲基甲酰胺 (DMF)加入到圓底烧瓶中 （三者的重量比见表 1 ), 加适量的 酸作催化剂， 160°C下回流 14h。 停止反应冷却后， 减压蒸馏除去 DMF 溶剂。 逐滴加入 80重量份环己酮中， 用上述方法洗涤 3次， 真空干燥， 得 到白色固体， 即碱可溶树脂。
光刻胶组合物的制备
根据表 1 所列举的组分和含量制备光刻胶组合物。 将所述组分充分搅 拌， 制成光刻胶组合物， 涂覆于具有黑矩阵的玻璃基板上， 标记为样品 4, 厚度为 2.6微米。 在 80-110°C烘箱中烘烤 3min, 用照度为 125mJ/cm2的紫 外光进行曝光处理后， 在室温下显影液中显影 30s, 经去离子水洗净后， 吹 干， 在 230°C的温度条件下烘烤 45min。
将玻璃切片、 制样， 扫描电子显微镜（SEM ) 测试截面、 观察坡度。 获得膜层的坡度角见图 7, 其中坡度角为 45.0° 。 可见膜层的坡度角较小， 能有效地避免漏光。 对比例
将实施例 4 中的光刻胶组合物中的碱可溶树脂的替换为同等重量百分 比的丙烯酸碱可溶树脂，其它组分和含量与实施例 4相同，制成光刻胶组合 物， 涂覆于具有黑矩阵的玻璃基板上， 标记为样品 5, 厚度为 2.6微米。 其 它步骤与实施例 4相同， 获得膜层的坡度角见图 7, 其中坡度角为 76.0° 。 可见膜层的坡度角较大， 容易漏光。
表 1 本发明实施例中各物质的重量比及光刻胶组合物的组分及其重量百分比 实施例 1 实施例 2 实施例 3 实施例 4 聚乙二醇： 1:0.6:50 1:0.5: 80 1:0.95:30 1: 0.8:70 己二酸活化物: N, N- 实施例中 二甲基甲酰胺溶剂
各反应物 含聚醚链的一元酸：
和溶剂的 丙蟑酸碱可 对脂：
重量比 N, N-二甲基甲酰胺 1:0.5:45 1:0.6:150 1:0.45:40 1:0.83:80 溶剂
实施例中所用的丙烯酸减可 ¾ ^对脂 高支化碱溶 胺改性环氧 芳香酸甲基 甲基丙烯 的种类 型丙烯酸化 丙烯酸酯 丙烯酸半酯 酸酯 聚酯
碱可溶树脂 7 12 24 15 双季成四醇 ：^ ¾四 四 乙氧化异戊 双季成四 光活性化合物 五丙烯酸酯， 丙烯酸酯， 22 四醇四丙蟑 醇六丙蟑
15 酸酯， 10 酸酯， 18 光致引发剂 安息香， 8 二苯甲酮， 1.3 蒽醌， 12.5 安息香， 4 光刻 a
合物部分
颜料分散液 48 60 50 69 组分的重
溶剂 环戊酮， 21 丙二酉享二乙 2-庚烷， 3 丙二酮甲 量比（ w % )
酸酯， 4.63 醚醋酸 酯， 8.88 添加剂 硅烷偶联剂， 抗氧剂 T501 , 偶氮二异丁 过氧化苯
1 0.07 酸二甲酯（紫 甲酰（交 外吸收剂）， 联剂）， 0.5 0.12 根据上述可见，与现有技术中含有甲基丙烯酸酯作为碱可溶树脂的光刻 胶组合物相比，含有根据本发明实施例制备的碱可溶树脂的光刻胶组合物所 制备的彩色膜层的坡度角较小，从而避免了彩色膜层和黑矩阵之间的连接容 易出现空隙而造成漏光的现象。此外，本发明实施例的光刻胶组合物改善了 后续工艺中液晶玻盒中取向层的涂覆及摩擦效果， 改善了液晶取向，从而提 高了画面的显示品质。
可以理解的是，以上实施方式仅仅是为了说明本发明的原理而采用的示 例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而 言， 在不脱离本发明的精神和实质的情况下， 可以做出各种变型和改进， 这 些变型和改进也视为本发明的保护范围。

Claims

权利要求书
1. 一种碱可溶树脂， 其中， 所述的碱可溶树脂为通过丙烯酸碱可溶树 脂与含聚醚链的一元酸接枝而制得的含聚醚链的丙烯酸碱可溶树脂。
2. 如权利要求 1所述的碱可溶树脂， 其中， 所述的含聚醚链的一元酸 结构式如
Figure imgf000014_0001
3. 如权利要求 1所述的碱可溶树脂， 其中， 所述的丙烯酸碱可溶树脂 包括甲基丙烯酸酯、胺改性丙烯酸酯、 多环芳侧基丙烯酸碱可溶树脂、 高支 化碱溶型丙烯酸化聚酯中的任意一种。
4. 如权利要求 1所述的碱可溶树脂， 其中， 所述的碱可溶树脂含有的 碳原子数小于 100。
5.一种如权利要求 1-4任一所述的碱可溶树脂的制备方法， 其包括如 下步骤：
1 )将己二酸、 1,3-二溴 -5,5-二甲基海因在溶剂二氯甲烷中反应获得 1- 溴己酸； 将 1-溴己酸与氢氧化钠反应获得 1-羟基己酸钠； 将 1-羟基己酸钠 与丙烯酰氯反应获得己二酸活化物；
2 )将聚乙二醇和己二酸活化物在溶剂 Ν,Ν-二甲基甲酰胺中进行反应获 得含聚醚链的一元酸；
3 )将含聚醚链的一元酸和丙烯酸碱可溶树脂在 Ν,Ν-二甲基甲酰胺溶剂 中进行反应获得所述含聚醚链的丙烯酸碱可溶树脂。
6. 如权利要求 5所述的碱可溶树脂的制备方法， 其中， 步骤 2中聚乙 二醇、 己二酸活化物的重量份数之比的范围为 1： 0.5至 1： 0.95。
7. 如权利要求 5或 6所述的碱可溶树脂的制备方法， 其中， 步骤 3中 含聚醚链的一元酸、 丙烯酸碱可溶树脂的重量份数之比的范围为 1： 0.45至 1： 0.83。
8. 一种光刻胶组合物， 包括如权利要求 1-4任一所述的碱可溶树脂。
9. 如权利要求 8所述的光刻胶组合物， 其中， 所述的光刻胶组合物， 包括以下重量百分比的组分：
碱可溶树脂： 7%-24%；
光活性化合物： 10%-22%；
光致引发剂： 1.3%-12.5%。
10. 如权利要求 9所述的光刻胶组合物， 其中， 所述光致引发剂包括安 息香类物质、 二苯甲酮类物质、 蒽醌类物质的一种或几种。
11.如权利要求 9或 10所述的光刻胶组合物， 其中， 所述光活性化合 物包括双季戊四醇五丙烯酸酯、双季戊四醇六丙婦酸酯、异戊四醇四丙婦酸 酯、 乙氧化异戊四醇四丙烯酸酯中的一种或几种。
12. 如权利要求 9-11任一所述的光刻胶组合物，还包括溶剂，所述溶剂 包括丙二酮甲醚醋酸酯、 丙二醇二乙酸酯、 3-乙氧基 -3-亚胺丙酸乙酯、 2- 庚烷、 3-庚烷、 环戊酮、 环己酮中的一种或几种。
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