WO2014134881A1 - 光刻胶用光敏性寡聚物、其制备方法及负性光刻胶组合物 - Google Patents

光刻胶用光敏性寡聚物、其制备方法及负性光刻胶组合物 Download PDF

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WO2014134881A1
WO2014134881A1 PCT/CN2013/076670 CN2013076670W WO2014134881A1 WO 2014134881 A1 WO2014134881 A1 WO 2014134881A1 CN 2013076670 W CN2013076670 W CN 2013076670W WO 2014134881 A1 WO2014134881 A1 WO 2014134881A1
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double bond
unsaturated double
monomer
parts
photosensitive oligomer
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PCT/CN2013/076670
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English (en)
French (fr)
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孙雯雯
张卓
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京东方科技集团股份有限公司
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Priority to US14/348,489 priority Critical patent/US9323151B2/en
Publication of WO2014134881A1 publication Critical patent/WO2014134881A1/zh

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    • 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
    • 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
    • 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
    • C08F220/10—Esters
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic 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
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • 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
    • G03F7/027—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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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

Definitions

  • Photosensitive oligomer for photoresist, preparation method thereof and negative photoresist composition Photosensitive oligomer for photoresist, preparation method thereof and negative photoresist composition
  • the present invention relates to a photosensitive oligomer for a photoresist, a process for producing the same, and a negative photoresist resin composition comprising the photosensitive oligomer.
  • Color filters are an important component of liquid crystal displays. Color filter technology is a key technology that must be mastered. Its technology focuses on the development of red, green and blue pigment photoresists and the development of coating processes. According to the chemical reaction mechanism and development principle of the photoresist, two types of negative glue and positive glue can be divided. Negative glue is formed when a chemical reaction occurs after light to form an insoluble matter; on the contrary, it is insoluble to some solvents, and is a positive gel after being irradiated to become a soluble substance.
  • the coating principle of the negative photoresist is: 1 firstly apply a photosensitive resin (ie, photoresist) on the surface of the object to be processed such as a glass substrate; 2 and then cover the desired processing pattern (and mask) on the resin. On the coating, exposure is then carried out; 3 The resin coating of the exposed portion undergoes a chemical crosslinking reaction, which causes a difference in developing performance between the exposed and unexposed resin portions due to chemical changes in the structure of the structure. That is, after exposure to an appropriate developer for development, the unexposed portion is washed away, and the exposed portion is left to form a shape opposite to that of the mask, i.e., a negative photoresist is obtained.
  • a photosensitive resin ie, photoresist
  • Embodiments of the present invention provide a photosensitive oligomer for photoresist which is excellent in performance.
  • Another embodiment of the present invention provides a method of preparing a photosensitive oligomer for a photoresist.
  • Still another embodiment of the present invention provides a negative photoresist resin composition containing a photosensitive oligomer for a photoresist.
  • a photosensitive oligomer for a photoresist comprising an unsaturated double bond group and a flexible group.
  • the monomer or compound for synthesizing the photosensitive oligomer is an organic acid monomer containing an unsaturated double bond, an organic ester monomer containing an unsaturated double bond, or an organic acid chloride monomer containing an unsaturated double bond/ A vinyl monomer, an alcohol compound containing an unsaturated double bond, and a silane/ether compound containing a flexible group.
  • the organic acid chloride monomer/ethylene monomer having an unsaturated double bond refers to an organic acid chloride monomer or an ethylene monomer containing an unsaturated double bond, and the vinyl monomer contains an ethyl group, which may participate in a polymerization reaction;
  • the silane/ether compound of the group means a silane compound and an ether compound, and both types of compounds contain a flexible group.
  • the photosensitive oligomer has a weight average molecular weight of from 500 to 5,000, for example from 1,000 to 2,500.
  • the amount of the monomer or compound used to synthesize the oligomer is:
  • a silane/ether compound containing a flexible group 3-20 parts A silane/ether compound containing a flexible group 3-20 parts.
  • the amount can be:
  • the photoresist is synthesized using a photosensitive oligomer according to the following method: an organic acid monomer having an unsaturated double bond, containing an unsaturated double bond, in the presence of a polymerization initiator at 50 to 80 ° C
  • the organic ester monomer, the organic acid chloride monomer/ethylene monomer are subjected to polymerization for 4-7 hours; then a polymerization inhibitor is added, the temperature is lowered to 40-60 ° C, and an alcohol compound containing an unsaturated double bond is added. And a silane/ether compound containing a flexible group is reacted.
  • the organic acid monomer having an unsaturated double bond (also referred to as a polymerizable double bond, an unsaturated bond) has at least one acidic group and at least one double bond group which can participate in the polymerization reaction.
  • the acidic group is a carboxyl group.
  • An example of the organic acid monomer having an unsaturated double bond is an unsaturated carboxylic acid compound having a double bond and a carboxyl group between conjugated carbons. There are no restrictions on the substituent of the organic acid monomer.
  • organic acid monomer (b-2) examples include, but are not limited to, selected from (indenyl)acrylic acid, crotonic acid, cinnamic acid, isocinnamic acid, ⁇ -mercaptocinnamic acid, and maleic acid. One or several of them.
  • (Mercapto) acrylic refers to mercaptoacrylic acid or acrylic acid, including derivatives of (fluorenyl) acrylic acid. Other unsaturated carboxylic acid compounds also include derivatives thereof.
  • the organic ester monomer (b-1) containing an unsaturated double bond is selected from the group consisting of decyl acrylate, decyl methacrylate, decyl decyl acrylate, ethyl methacrylate, propyl methacrylate, hydrazine.
  • Dibutyl acrylate One or more of an ester, isobutyl methacrylate or isoamyl acrylate.
  • the organic ester monomer having an unsaturated double bond has at least one double bond group and at least one ester group functional group which can participate in the polymerization reaction.
  • organic ester monomers examples include (meth) acrylates and derivatives thereof, including but not limited to methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, One or more of butyl (meth)acrylate, isobutyl (meth)acrylate or isoamyl acrylate.
  • the (meth) acrylates represent acrylates and methacrylates.
  • the methyl (meth) acrylate represents methyl acrylate and methyl methacrylate.
  • the organic acid chloride monomer/ethylene monomer (b-3) containing an unsaturated double bond is selected from the group consisting of styrene, butadiene, maleic acid (MA), ethacryloyl chloride, acryloyl chloride, One or more of isobutylacryloyl chloride.
  • the vinyl monomer is an olefin monomer containing at least one double bond.
  • examples of the vinyl monomer include, but are not limited to, styrene, butadiene, maleic acid, ethyl ethoxylate, vinyl acetate, and the like.
  • the organic acid chloride-based monomer having an unsaturated double bond is a double bond group and at least one acid chloride group containing at least one which can participate in a polymerization reaction.
  • the organic acid chloride-based monomer include, but are not limited to, (meth)acryloyl chloride and derivatives thereof.
  • the organic acid chloride-based monomer includes one or more selected from the group consisting of (meth)acryloyl chloride, 2-ethylacryloyl chloride, and 2-isobutylacryloyl chloride.
  • the (meth)acryloyl chloride and its derivatives represent acryloyl chloride and its derivatives and methacryloyl chloride and its derivatives.
  • the alcohol compound containing an unsaturated double bond is a double bond group containing at least one hydroxyl group and at least one polymerizable reaction.
  • the alcohol compound is allyl alcohol, dipentenol or triethylene glycol.
  • the flexible group-containing compound has at least one flexible group and at least one functional group reactive with the oligomer side chain group.
  • the flexible groups include, but are not limited to, silane groups, ether groups.
  • the compound containing a flexible group includes a silane compound and an ether compound (b-5).
  • ether compound examples include, but are not limited to, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, anisole, and the like.
  • the silane compound is selected from the group consisting of ( ⁇ , ⁇ -diphenylethyl-3-aminopropyl)trimethoxysilane, 1,3-bis(trimethylsilyl)urea, 3-(3-1 ⁇ 2 benzene) Oxy) propyltrimethylsilane, 3-aminophenylpropyltriethylsilane, phenylpropyltrimethylsilane, 3-aminopropylbenzyldiethylsilane, hydrazine, hydrazine-bis(3-chloro-2-hydroxyl) Phenylpropyl)propyltriethoxysilane, hydrazine, hydrazine-dimethylaminochlorodiphenylsilane, tris(dimethylamino)silane, trihexylazidosilane, bis(trimethoxysilyl) One or more of propyl)amines and the like.
  • the photosensitive ⁇
  • the polymerization initiator is 2, 2,-azobis-2-mercaptobutyronitrile, dinonyl azobisisobutyrate or azobisisoheptanenitrile in an amount of 0.5 to 5 parts.
  • the organic acid monomer (b-2) includes, but is not limited to, one of (mercapto)acrylic acid, crotonic acid, cinnamic acid, isocinnamic acid, ⁇ -mercaptocinnamic acid, and maleic acid. Or several. It is added in an amount of 15-35 parts, for example, 20-30 parts.
  • the organic ester monomer includes, but is not limited to, (decyl) decyl acrylate, (mercapto) ethyl acetoacetate, (mercapto) propyl acrylate, butyl (meth) acrylate, ( One or more of isobutyl acrylate or isoamyl acrylate. It is added in an amount of 10-20 parts, for example 15-20 parts.
  • the organic acid chloride monomer/ethylene monomer (b-3) includes, but is not limited to, styrene, butadiene, maleic acid (MA), ethacryloyl chloride, acryloyl chloride or different One or more of butyl acryloyl chloride. It is added in an amount of 50-80 parts, for example, 65-75 parts.
  • the polymerization inhibitor includes, but is not limited to, hydroquinone, 2-sec-butyl-4,6-dinitrophenol, p-tert-butyl catechol, 2,5-di-tert-butyl hydroquinone At least one of them is added in an amount of 0.5 to 3 parts.
  • the alcohol compound includes, but is not limited to, allyl alcohol, dipentenol or triethylene glycol. It is added in an amount of 10-20 parts, for example, 10-15 parts.
  • the ether compound includes, but is not limited to, propylene glycol monoterpene ether acetate, diethylene glycol dioxime ether, benzoin ether, and the like.
  • the silane compound is selected from the group consisting of ( ⁇ , ⁇ -diphenylethyl-3-aminopropyl)trimethoxysilane, 1,3-bis(tris-decylsilyl)urea, 3-aminophenylpropyl Triethoxysilane, 3-aminophenylpropyltrimethoxysilane, 3-aminopropylphenylhydrazinediethylsilane, hydrazine, hydrazine-bis(3-chloro-2-hydroxyphenylpropyl)aminopropyl Triethyl silane, hydrazine, hydrazine-diguanidine aminochlorodiphenyl silane, tris(di- tt) silane, trihex
  • the monomer needs to be dissolved in an organic solvent, which is propylene glycol oxime ether acetate, ethyl 3-ethoxypropionate, ethylene glycol ether, ethyl acetate, acetic acid. Propyl ester and the like.
  • Step 2) The alcohol compound and the silane/polymerizable ether compound are gradually added in batches, for example If used, add five equal parts at intervals of one aliquot per hour.
  • the photosensitive oligomer of the embodiment of the present invention has an unsaturated functionality of 3-7.
  • a negative photoresist resin composition comprising the photosensitive oligomer is also provided.
  • the negative photoresist resin composition includes the following components by weight:
  • Alkali-soluble resin 5-14.5 parts
  • the negative photoresist resin composition includes the following components by weight:
  • Alkali-soluble resin 7-12 parts
  • the alkali-soluble resin is aryl decyl acrylate (SB401), a trifunctional water-soluble acrylate, a tetrafunctional aqueous aromatic PEA, a water-soluble polyethylene glycol diacrylate, or the like.
  • the photoinitiator comprises an initiator selected from the group consisting of initiator 369, initiator 379, 2-mercapto-1-[4-(indolyl)phenyl]-2-monolobin propan-1-one, nitroaniline, At least one of hydrazine, benzophenone, and N-acetyl-4-nitronaphthylamine.
  • the chemical name of the initiator 369 is 2-phenylbenzyl-2-didecylamine-1-(4-morpholiniumbenzyl)butanone
  • the chemical name of the initiator 379 is 2-(4-fluorenyl) Benzyl)-2-(didecyl tt)-l-(4-morpholinylphenyl)-1-butanone
  • the organic solvent are propylene glycol oxime ether acetate (PMA) or ethyl 3-ethanepropionic acid.
  • the desired pigment can be selected depending on the color filter color, such as red, green, and blue pigments well known in the art.
  • the negative photoresist resin composition of the embodiment of the present invention further includes some other auxiliary agents, such as a dispersing agent, a leveling agent or an antifoaming agent, etc., the mass of the dispersing agent occupies the total mass of the negative resist resin composition. 0.2% to 5%; the quality of the leveling agent is 0.2% to 5% of the total mass of the negative photoresist resin composition; the quality of the defoaming agent is the total mass of the negative photoresist resin composition 0.1%-3%.
  • auxiliary agents such as a dispersing agent, a leveling agent or an antifoaming agent, etc.
  • the photosensitive oligomer for photoresist used in the embodiment of the present invention is added with a flexible functional group during synthesis.
  • Groups such as siloxy, carboxy, carbon silicon, etc. or their functional groups containing carbon-carbon double bonds, provide a buffer for the interior of the photoresist after completion of various process steps, avoiding surface collapse Equal surface defects. That is, by adding a flexible group side chain to the polymerizable oligomer in the photoresist component, the existing unevenness or agglomeration is improved, and the surface unevenness caused by the film thickness reduction is alleviated, so that the photoresist is The formed surface is flat and the chromaticity is displayed evenly.
  • the negative photoresist resin composition containing the photosensitive oligomer in the embodiment of the present invention is formed into a photoresist coating liquid, coated on a transparent substrate to form a predetermined pattern and a film thickness, and after drying, using ultraviolet rays
  • the exposure and masking device are exposed, and developed with an alkali-soluble solution, and the obtained image pattern has a uniform boundary and a smooth surface.
  • MAA maleic acid
  • MA 15 g decyl acrylate
  • AMBN polymerization initiator 2, 2,-azobis-2-mercaptobutyronitrile
  • Step 2 3 g of allyl alcohol and 10 g of a mixture of hydrazine-diphenylethyl-3-aminopropyltrioxane were added dropwise to the reaction system through a constant pressure dropping funnel at intervals of one aliquot per hour. Five aliquots were added to form a mercaptoacrylic acid ( ⁇ ) / maleic acid ( ⁇ ) / decyl acrylate terpolymer having an unsaturated double bond and a flexible silane group in the side chain, and reacted for 7 hours. The temperature was lowered, and a white powder was precipitated in a large amount of sterol/water (1:1 volume ratio) solution, suction-filtered, and vacuum-dried for 6 hours to obtain a photosensitive oligomer B-l.
  • the photosensitive oligomer had a weight average molecular weight of 2,000 as measured by gel permeation chromatography (GPC; dissolution solvent tetrahydrofuran).
  • Second step 140g solvent propylene glycol oxime ether acetate (PMA), 20 g thioglycolic acid (MAA), 60 g of styrene, 15 g of decyl acrylate (MAC) and 8 g of polymerization initiator 2, 2'-azobis-2-mercaptobutyronitrile ( ⁇ ) added with condenser, stirrer, constant pressure
  • PMA solvent propylene glycol oxime ether acetate
  • MAA thioglycolic acid
  • MAC decyl acrylate
  • ⁇ polymerization initiator 2'-azobis-2-mercaptobutyronitrile
  • the second step 3g of allyl alcohol and 20g of hydrazine-diphenylethyl-3-aminopropyltrioxane silane mixture were added dropwise to the reaction system through a constant pressure dropping funnel at intervals of one aliquot per hour. Five aliquots were added to form a mercaptopropene/phenethyl acrylate/decyl acrylate terpolymer having a double bond, a silane group, and a hydroxyl group in the side chain, and reacted for 5 hours. The temperature was lowered, and a white powder was precipitated in a large amount of sterol/water (1:1 volume ratio) solution, suction-filtered, and vacuum-dried for 6 hours to obtain a photosensitive oligomer ⁇ -2.
  • the photosensitive oligomer had a weight average molecular weight of 1,800 as measured by gel permeation chromatography (GPC; dissolution solvent tetrahydrofuran).
  • MAA 60 g of styrene, 15 g of decyl acrylate (MAC) and 8 g of polymerization initiator 2, 2'-azobis-2-mercaptobutyronitrile (AMBN) added with condenser, stirrer, constant pressure
  • MAC decyl acrylate
  • AMBN 2'-azobis-2-mercaptobutyronitrile
  • the second step 3 g of allyl alcohol and 15 g of hydrazine, hydrazine-diphenylethyl-3-aminopropyltrimethylsilane and 5 g of 3-(3-aminophenoxyl) were added dropwise to the reaction system through a constant pressure dropping funnel. a mixture of propyltrimethoxysilane, adding five equal parts at intervals of one aliquot per hour to form a mercaptopropene/benzophenone/acrylic acid oxime with a double bond, a silane group, and a hydroxyl group in the side chain. The ester terpolymer was reacted for 4 hours. The temperature was lowered, and a white powder was precipitated in a large amount of sterol/water (1:1 volume ratio) solution, suction-filtered, and vacuum-dried for 6 hours to obtain a photosensitive oligomer B-3.
  • the polymerizable oligomer had a weight average molecular weight of 1,100 as measured by gel permeation chromatography (GPC; dissolution solvent tetrahydrofuran).
  • the number of amine-containing groups was measured by acid direct titration to be 5.
  • the photosensitive oligomer was prepared by the polymerization method of Example 1, wherein the difference was in the polymerization monomer and the amount, see ⁇ 2.
  • alkali-soluble resin SB 401 manufactured by Basf Co., Ltd.
  • initiator 369 manufactured by Basf Co., Ltd.
  • pigment CI254 3-ethoxypropane was added.
  • the acid ethyl ester solution organic solvent was dissolved and mixed by a magnetic stirrer to prepare a photosensitive resin composition for a color filter.
  • the specific components are shown in Table 3.
  • the method of the comparative example is the same as that of Example 11, and the specific components are shown in Table 3, wherein the oligomer used in Comparative Example 1 is pentaerythritol tetraacrylate, and the oligomer used in Comparative Example 2 is dipentaerythritol hexaacrylate, Comparative Example 3
  • the oligomer used was trishydroxypropyl propane triacrylate. Evaluation method
  • Alkali resistance The photosensitive resin layer is measured for its transmittance at a wavelength of 400-700 nm, and then placed in 2% NaOH for 5 minutes, and then the transmittance is measured at a wavelength of 400-700 nm, according to The light transmittance change ratio was evaluated on the following basis.
  • Residue Spin-coat photosensitive resin to 3um, pre-bake at 90 °C for 3min, irradiate with ultraviolet light, then immerse in 23 °C developer for 2min development, remove the unexposed part, wash with pure water, After baking at 200 ° C for 40 min, a desired photosensitive resin pattern was formed, and it was observed by an electron microscope to determine whether or not a residue was present on the surface.
  • the negative photoresist composition containing the photosensitive oligomer in the embodiment of the present invention has a pattern boundary and a smooth surface after being formed into a photoresist coating liquid, after exposure and development.

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Abstract

本发明的实施例提供了一种光刻胶用光敏性寡聚物，所述光敏性寡聚物含有不饱和双键基团和柔性基团，合成所述光敏性寡聚物的单体或化合物为含有不饱和双键的有机酸类单体、含有不饱和双键的有机酯类单体、含有不饱和双键的有机酰氯类单体/乙烯类单体、含有不饱和双键的醇类化合物和含有柔性基团的硅烷类/醚类化合物。本发明还提供一种含有光敏性寡聚物的负性光刻胶树脂组合物。

Description

光刻胶用光敏性寡聚物、 其制备方法及负性光刻胶组合物 技术领域
本发明涉及一种光刻胶用光敏性寡聚物、 其制备方法以及包含该光敏性 寡聚物的负性光刻胶树脂组合物。
背景技术
彩色滤光片是液晶显示器的重要组成部件， 彩色滤光片技术是必须掌握 的关键技术， 其技术重点在于红、 绿、 蓝颜料光刻胶的研制和涂布工艺的研 发。 根据光刻胶化学反应机理和显影原理， 可分负性胶和正性胶两类。 光照 后发生化学反应生成不溶性物质的即为负性胶； 反之， 对某些溶剂是不可溶 的， 经光照后变成可溶物质的即为正性胶。
负性光刻胶的涂布原理是： ①首先将感光性树脂 （即光刻胶）涂布在玻 璃基板等被加工物体表面； ②再将所需加工图形 （及掩膜板）覆盖在树脂涂 层上， 然后进行曝光； ③曝光部分的树脂涂层发生化学交联反应， 由于自身 结构的化学变化， 使曝光与未曝光树脂部分在显影性能方面产生差异。 即曝 光后经适当显影液显影后， 未曝光部分被洗掉， 而曝光部分被保留， 形成与 掩膜板相反的形状， 即得负性光刻胶。
但在实际实验及应用过程中往往会发现： 光刻胶经曝光、 显影或后烘后， 图案的表面出现坑洼状、 不平整或结块现象。 因此， 需要进一步研究及筛选 负性光刻胶树脂组合物的组分， 以解决表面塌陷等缺陷。
发明内容
本发明的实施例提供了一种性能优良的光刻胶用光敏性寡聚物。
本发明的另一个实施例提供了光刻胶用光敏性寡聚物的制备方法。
本发明的又另一个实施例提供了含有光刻胶用光敏性寡聚物的负性光刻 胶树脂组合物。
在本发明的一个实施方式中， 提供了一种光刻胶用光敏性寡聚物， 所述 光敏性寡聚物含有不饱和双键基团和柔性基团。 合成所述光敏性寡聚物的单 体或化合物为含有不饱和双键的有机酸类单体、 含有不饱和双键的有机酯类 单体、 含有不饱和双键的有机酰氯类单体 /乙烯类单体、 含有不饱和双键的醇 类化合物和含有柔性基团的硅烷类 /醚类化合物。 其中不饱和双键的有机酰氯类单体 /乙烯类单体指含有不饱和双键的有机 酰氯类单体或乙烯类单体， 乙烯类单体含有乙婦基， 可以参与聚合反应； 含 有柔性基团的硅烷类 /醚类化合物指硅烷类化合物和醚类化合物， 两类化合物 均包含柔性基团。
其中所述光敏性寡聚物的重均分子量为 500-5000 , 例如 1000-2500。
合成所述寡聚物所用的单体或化合物的用量为：
含有不饱和双键的有机酸类单体 15-35份；
含有不饱和双键的有机酯类单体 10-20份；
含有不饱和双键的有机酰氯类单体 /乙烯类单体 50-80份；
含有不饱和双键的醇类化合物 10-20份； 和
含有柔性基团的硅烷类 /醚类化合物 3-20份。
例如， 用量可以为：
含有不饱和双键的有机酸类单体 20-30份；
含有不饱和双键的有机酯类单体 15-20份；
含有不饱和双键的有机酰氯类单体 /乙烯类单体 65-75份；
含有不饱和双键的醇类化合物 10- 15份；
含有柔性基团的硅烷类 /醚类化合物 10-15份。
在一个方面， 光刻胶用光敏性寡聚物根据如下方式合成： 在 50-80°C、 聚 合引发剂存在下， 先将含有不饱和双键的有机酸类单体、 含有不饱和双键的 有机酯类单体、有机酰氯类单体 /乙烯类单体进行聚合反应 4-7小时； 然后加入 阻聚剂， 降温至 40-60°C , 再加入含有不饱和双键的醇类化合物及含有柔性基 团的硅烷类 /醚类化合物进行反应。
所述的含有不饱和双键（或称为可聚合双键、 不饱和键） 的有机酸类单 体具有至少一个酸性基团和至少一个可参与聚合反应的双键基团。 例如， 所 述酸性基团为羧 ½团。 所述含有不饱和双键的有机酸类单体的例子为在共 轭碳之间具有双键和羧基的不饱和羧酸化合物。 对有机酸类单体取代基没有 限制。 所述有机酸类单体（b-2 )的具体实施例包括， 但不限于， 选自 （曱基） 丙烯酸、 巴豆酸、 肉桂酸、异肉桂酸、 α-曱基肉桂酸、马来酸中的一种或几种。
(曱基）丙烯酸指曱基丙烯酸或丙烯酸， 包括（曱基） 丙烯酸的衍生物。 其他不饱和羧酸化合物也包括其衍生物。
所述含有不饱和双键的有机酯类单体（b-1 )是选自丙烯酸曱酯、 丁烯酸 曱酯、 曱基丙烯酸曱酯、 曱基丙烯酸乙酯、 曱基丙烯酸丙酯、 曱基丙烯酸丁 酯、 甲基丙烯酸异丁酯或丙烯酸异戊基酯中的一种或几种。 所述含有不饱和 双键的有机酯类单体具有至少一个可参与聚合反应的双键基团和至少一个酯 基官能团。 所述有机酯类单体的例子为 （甲基） 丙烯酸酯类及其衍生物， 包 括但不限于（甲基） 丙烯酸甲酯、 （甲基） 丙烯酸乙酯、 （甲基） 丙烯酸丙酯、 (甲基）丙烯酸丁酯、 （甲基）丙烯酸异丁酯或丙烯酸异戊酯中的一种或几种。 所述（甲基） 丙烯酸酯类表示丙烯酸酯类和甲基丙烯酸酯类。 所述（甲基） 丙烯酸甲酯表示丙烯酸甲酯和甲基丙烯酸甲酯。
所述含有不饱和双键的有机酰氯类单体 /乙烯类单体（ b-3 )为选自苯乙烯、 丁二烯、 顺丁烯二酸（MA )、 乙基丙烯酰氯、 丙烯酰氯、 异丁基丙烯酰氯中 的一种或几种。
所述乙烯类单体为包含至少一个双键的烯烃类单体。 所述乙烯类单体的 例子包括但不限于苯乙烯、 丁二烯、 顺丁烯二酸、 乙婦基醚、 醋酸乙烯酯及 其它们的^[ 生物。
所述含有不饱和双键的有机酰氯类单体为含有至少一个可参与聚合反应 的双键基团和至少一个酰氯基团。 所述有机酰氯类单体的例子包括但不限于 (甲基） 丙烯酰氯及其衍生物。 例如， 所述有机酰氯类单体包括选自 （甲基） 丙烯酰氯、 2-乙基丙烯酰氯、 2-异丁基丙烯酰氯中的一种或几种。所述（甲基） 丙烯酰氯及其衍生物表示丙烯酰氯及其衍生物和甲基丙烯酰氯及其衍生物。
所述含有不饱和双键的醇类化合物为含有至少一个羟基和至少一个可参 与聚合反应的双键基团。 例如， 所述醇类化合物为烯丙醇、 二戊烯三醇或三 乙烯二醇。
所述含有柔性基团化合物具有至少一个柔性基团和至少一个可与寡聚物 侧链基团反应的功能基团。 所述柔性基团包括但不限于硅烷基团、 醚类基团。 例如， 所述含有柔性基团化合物包括硅烷类化合物和醚类化合物（b-5 )。
所述醚类化合物的例子包括但不限于丙二醇一甲醚乙酸酯、 二甘醇二甲 醚、 苯甲醚等。
所述硅烷类化合物是选自（Ν,Ν-二苯乙基 -3-氨基丙基)三甲氧基硅烷、 1,3- 双 (三甲代甲硅烷基)脲、 3- ( 3-½苯氧基） 丙基三甲 硅烷、 3-氨基苯丙 基三乙 甲硅烷、 苯丙基三甲 硅烷、 3-氨基丙基苯甲基二乙 硅烷、 Ν,Ν-二 (3-氯 -2-羟基苯丙基) 丙基三乙氧基甲硅烷 、 Ν,Ν-二甲氨基 氯代二苯基硅烷、 三 (二甲氨基)硅烷、 三己基叠氮基硅烷、 二 (三甲氧基甲硅 烷基丙基）胺等中一种或几种。 在一个方面， 所述光敏性寡聚物结构单元包括柔性基团和可聚合基团， 并且可例如通过如下方法制备：
1 )在 50-80°C、 聚合引发剂存在下， 先将含有不饱和双键的有机酸类单 体、 含有不饱和双键的有机酯类单体、 含有不饱和双键的有机酰氯类单体 /乙 烯类单体进行聚合反应 4-7小时；
2 ) 然后加入阻聚剂， 降温至 40-60 °C , 再加入含有不饱和双键的醇类化 合物及含有柔性基团的硅烷类 /醚类化合物进行反应。
其中所述聚合引发剂为 2, 2，-偶氮双 -2-曱基丁腈、 偶氮二异丁酸二曱酯、 偶氮二异庚腈， 其加入量为 0.5-5份。
例如， 所述有机酸类单体（b-2 ) 包括， 但不限于， （曱基） 丙烯酸、 巴 豆酸、 肉桂酸、 异肉桂酸、 α-曱基肉桂酸、 马来酸中的一种或几种。 其加入量 为 15-35份， 例如 20-30份。
例如， 所述有机酯类单体包括， 但不限于， （曱基）丙烯酸曱酯、 （曱基） 丙婦酸乙酯、 （曱基）丙烯酸丙酯、 （曱基）丙烯酸丁酯、 （曱基）丙烯酸异丁 酯或丙烯酸异戊酯中的一种或几种。 其加入量为 10-20份， 例如 15-20份。
例如， 所述有机酰氯类单体 /乙烯类单体（b-3 )包括，但不限于， 苯乙烯、 丁二烯、 顺丁烯二酸（MA )、 乙基丙烯酰氯、 丙烯酰氯或异丁基丙烯酰氯中 的一种或几种。 其加入量为 50-80份， 例如 65-75份。
所述阻聚剂包括， 但不限于， 对苯二酚、 2-仲丁基 -4, 6-二硝基苯酚、 对 叔丁基邻苯二酚、 2, 5-二特丁基对苯二酚中的至少一种， 其加入量为 0.5-3份。
例如， 所述醇类化合物包括， 但不限于， 烯丙醇、 二戊烯三醇或三乙烯 二醇。 其加入量为 10-20份， 例如 10-15份。
例如， 所述醚类化合物包括但不限于丙二醇一曱醚乙酸酯、 二甘醇二曱 醚、 苯曱醚等。 所述硅烷类化合物选自 （Ν,Ν-二苯乙基 -3-氨基丙基)三曱氧基 硅烷、 1,3-双 (三曱代曱硅烷基)脲 、 3-氨基苯丙基三乙氧基曱硅烷 、 3-氨基 苯丙基三曱氧基硅烷、 3-氨基丙基苯曱基二乙 硅烷、 Ν,Ν-二 (3-氯 -2-羟基 苯丙基)氨基丙基三乙 曱硅烷 、 Ν,Ν-二曱氨基氯代二苯基硅烷、 三 (二曱 tt)硅烷、 三己基叠氮基硅烷、 二 (三曱氧基曱硅烷基丙基）胺等中一种或几 种。 其加入量为 3-20份， 例如 10-15份。
步骤 1 ) 中聚合反应时， 单体需要先溶于有机溶剂中， 所述有机溶剂为丙 二醇曱醚醋酸酯、 3-乙氧基丙酸乙酯、 乙烯乙二醇醚、醋酸乙酯、醋酸丙酯等。
步骤 2 )中醇类化合物及硅烷类 /可聚合醚类化合物采用分批逐步加入，例 如采用以每小时一等份的量间隔添加五等份。
本发明实施例的光敏性寡聚物的不饱和官能度为 3-7。
在本发明的另一个实施方式中， 还提供包含所述光敏性寡聚物的负性光 刻胶树脂组合物。
所述负性光刻胶树脂组合物包括如下重量份的组分：
碱溶性树脂 5-14.5份；
光敏性寡聚物 4-10份；
光引发剂 1-5.5份；
有机溶剂 30-70份； 和
颜料 5-20份。
例如， 所述负性光刻胶树脂组合物包括如下重量份的组分：
碱溶性树脂 7-12份；
光敏性寡聚物 5-8份；
光引发剂 2-4.5份；
有机溶剂 40-60份；
颜料 10-15份。
其中， 所述碱溶性树脂为芳香酸曱基丙烯酸曱酯（SB401 )、 三官能度水 溶性丙烯酸酯、 四官能度水性芳香族 PEA、 水溶性聚乙二醇双丙烯酸酯等。
所述光引发剂包括选自引发剂 369、 引发剂 379、 2-曱基 -1- [ 4- (曱石克基） 苯基] -2-单叶素丙烷 -1-酮、 硝基苯胺、 蒽醌、 二苯曱酮、 N-乙酰 -4-硝基萘胺 中的至少一种。 其中， 引发剂 369的化学名称为 2-苯基苄 -2-二曱基胺 -1- ( 4-吗 啉苄苯基）丁酮，引发剂 379的化学名称为 2-(4-曱基苄基) -2- (二曱基 tt)-l-(4- 吗啉苯基) -1-丁酮。 所述有机溶剂的例子为丙二醇曱醚醋酸酯（PMA )或 3-乙 氣基丙酸乙酯。
可以依据彩色滤光片色彩选择需要的颜料， 比如本领域熟知的红、 绿、 蓝颜料。
本发明实施例的负性光刻胶树脂组合物还包括一些其他助剂， 比如分散 剂、 流平剂或消泡剂等， 所述分散剂的质量占负性光刻胶树脂组合物总质量 的 0.2%-5%； 所述流平剂的质量占负性光刻胶树脂组合物总质量的 0.2%-5%； 所述消泡剂的质量占负性光刻胶树脂组合物总质量的 0.1%-3%。上述助剂可采 用本领域技术人员熟知的。
本发明实施例所述的光刻胶用光敏性寡聚物在合成时， 加入柔性官能基 团， 如硅氧基、 碳氧基、 碳硅等或其含碳碳双键的官能基团， 使其在完成各 工艺环节后为光刻胶内部提供一种緩沖作用， 避免其出现表面塌陷等表面缺 陷。 即通过光刻胶组份中的可聚合寡聚物上添加柔性基团侧链对现有不平整 或结块等不良现象进行改进， 緩解因膜厚减小造成的表面不平， 使光刻胶形 成的表面平整， 色度均匀显示。
本发明实施例的含有所述光敏性寡聚物的负性光刻胶树脂组合物制成光 刻胶涂布液， 涂布在透明基板上， 形成规定图案及膜厚， 干燥后， 利用紫外 曝光及掩膜装置进行曝光， 并利用碱溶性溶液进行显影， 获得的显像图案边 界整齐、 表面平整。 具体实施方式
以下实施例用于说明本发明， 但不用来限制本发明的范围。 实施例 1光敏性寡聚物的合成
第一步： 将 120g 溶剂丙二醇曱醚醋酸酯 （PMA )、 20 g 曱基丙烯酸
( MAA )、 70g顺丁烯二酸（也称马来酸， MA )、 15 g丙烯酸曱酯（MAC ) 和 8g聚合引发剂 2, 2，-偶氮双 -2-曱基丁腈（AMBN )加入带有冷凝管、 搅 拌器、 恒压滴液漏斗和温度计的四口瓶中， 通入氮气保护， 升温至 50°C , 反 应 5h, 加入 4g阻聚剂对苯二酚， 降温至 40°C , 进行第二步反应。
第二步： 通过恒压滴液漏斗向反应体系中滴加 3g烯丙醇与 10g Ν,Ν-二 苯乙基 -3-氨基丙基三曱 硅烷混合物， 以每小时一等份的量间隔添加五等 份， 形成侧链上带有不饱和双键、 柔性硅烷基团的曱基丙烯酸（ΜΑΑ ) /马 来酸（ΜΑ ) /丙烯酸曱酯三元共聚物，反应 7小时。 降温，在大量曱醇 /水（1 : 1体积比）溶液中析出白色粉末， 抽滤， 真空干燥 6小时， 即得光敏性寡聚 物 B-l。
经凝胶渗透色谱法（GPC; 溶出溶媒四氢呋喃）测定， 光敏性寡聚物的 重均分子量为 2000。
通过酸直接滴定法（过程为： 在乙醇溶剂中， 以曱基红为指示剂， 用盐 酸标准溶液进行滴定）， 测含胺类基团官能数为 6。 实施例 2光敏性寡聚物的合成
第一步： 将 140g 溶剂丙二醇曱醚醋酸酯 （PMA )、 20 g 曱基丙烯酸 ( MAA )、 60g苯乙烯、 15 g丙烯酸曱酯（MAC )和 8g聚合引发剂 2, 2'- 偶氮双 -2-曱基丁腈（ΑΜΒΝ )加入带有冷凝管、 搅拌器、 恒压滴液漏斗和温 度计的四口瓶中， 通入氮气保护， 升温至 60°C , 反应 7h, 加入 4g阻聚剂对 苯二酚， 降温至 50°C , 进行第二步反应。
第二步： 通过恒压滴液漏斗向反应体系中滴加 3g烯丙醇与 20g Ν,Ν-二 苯乙基 -3-氨基丙基三曱 硅烷混合物， 以每小时一等份的量间隔添加五等 份， 形成侧链上带有双键、 硅烷基团、 羟基的曱基丙烯^/苯乙婦 /丙烯酸曱 酯三元共聚物， 反应 5小时。 降温， 在大量曱醇 /水（1 : 1体积比）溶液中 析出白色粉末， 抽滤， 真空干燥 6小时， 即得光敏性寡聚物 Β-2。
经凝胶渗透色谱法（GPC; 溶出溶媒四氢呋喃）测定， 光敏性寡聚物的 重均分子量为 1800。
通过酸直接滴定法， 测含胺类基团官能数为 5。 实施例 3光敏性寡聚物的合成
第一步： 将 120g 溶剂丙二醇曱醚醋酸酯 （PMA )、 20 g 曱基丙烯酸
( MAA )、 60g苯乙烯、 15 g丙烯酸曱酯（MAC )和 8g聚合引发剂 2, 2'- 偶氮双 -2-曱基丁腈（AMBN )加入带有冷凝管、 搅拌器、 恒压滴液漏斗和温 度计的四口瓶中， 通入氮气保护， 升温至 80°C , 反应 4h, 加入 4g阻聚剂对 苯二酚， 降温至 60°C , 进行第二步反应。
第二步： 通过恒压滴液漏斗向反应体系中滴加 3g烯丙醇与 15g Ν,Ν-二 苯乙基 -3-氨基丙基三曱 硅烷、 5g 3- ( 3-氨基苯氧基） 丙基三曱氧基硅烷 混合物， 以每小时一等份的量间隔添加五等份， 形成侧链上带有双键、 硅烷 基团、 羟基的曱基丙烯^/苯乙婦 /丙烯酸曱酯三元共聚物， 反应 4 小时。 降 温， 在大量曱醇 /水（1: 1体积比）溶液中析出白色粉末， 抽滤， 真空干燥 6 小时， 即得光敏性寡聚物 B-3。
经凝胶渗透色谱法（GPC; 溶出溶媒四氢呋喃）测定， 可聚合寡聚物的 重均分子量为 1100。
通过酸直接滴定法， 测含胺类基团官能数为 5。
采用实施例 1的相同方法获得光敏性寡聚物 B-4、 B-5, 即实施例 4-5。 对于聚合寡聚物的单体种类和用量及加料方式有所差别， 具体见表 1。 表 1 光敏性寡聚物 （单位 g ) 光敏 聚合用单体
性寡 (b-1) (b-4) (b-2) (b-3) (b-5) 加料 不饱和 分子量 聚物 SM或 方式 官能度
MAC 丙烯醇 MAA b-5-1 b-5-2 b-5-3
MA
B-1 15 15 20 70 10 连续 2000 6
B-2 15 15 20 60 20 连续 1800 5
B-3 15 15 20 60 15 5 连续 1100 5
B-4 15 15 30 60 10 连续 1500 5
B-5 15 15 30 60 10 一次性 1200 4 注： 其它两种合成单体以 1: 1重量份比， 并为上述三种单体总量的 30%参与反应。 其中， 连续加料相 对于一次性加料， 对单体的利用率更高。
MAA-甲基丙烯酸
SM-苯乙烯
b-5-l: (Ν,Ν-二苯乙基 -3-氨基丙基）三甲氧基硅烷
b-5-2: 3- 苯氧基） 丙基三甲氧基硅烷
b-5-3: 三 (二甲氣基)娃坑 实施例 6-10
采用实施例 1的聚合方法制备光敏性寡聚物， 其中不同的是聚合单体及用 量， 具体见 ^2。
表 2 光敏性寡聚物 （单位 g )
光敏 聚合用单体 不饱 加料
性寡 (b-1) 分子量 和官
(b-4) (b-2) (b-3) (b-5) 方式 聚物 HbSL
25g丙埽 10g婦丙 15g肉桂 70g苯乙 10g二 (三甲氧基甲硅
B-6 连续 1800 5 酸甲酯 醇 酸 烯 烷基丙基 )胺
25g甲基 15ga-甲 70g乙基
15g埽丙 10gl,3-双 (三甲代甲
B-7 丙烯酸 基肉桂 丙烯酸 连续 1400 5 醇 硅烷基)脲
甲酯 酸 酰氯
25g甲基 15g异肉 70g异丁
20g婦丙
B-8 丙烯酸 桂酸 基丙烯 10g二甘醇二甲醚 连续 1200 4 醇
丁酯
25g甲基 15g巴豆
15g二戊 60g丙埽 10g 二丙烯基乙
B-9 丙烯酸 酸 连续 1400 4 烯三醇 二醇甲基醚
乙酯
25g甲基 15g甲基
15g三乙 70g丁二 10g乙二醇一甲醚乙
B-10 丙烯酸 丙烯酸 连续 1500 6 烯二醇 烯 酸酯
异丁酯 实验例 11-14 负性光刻胶树脂组合物
使用前述合成的光敏性寡聚物（分别为实施例 1-5 )、碱溶性树脂 SB 401 ( basf 公司生产 )、 引发剂 369 ( basf 公司生产 ), 颜料 C.I.254, 加入 3-乙氧 基丙酸乙酯溶液（有机溶剂）， 以磁力搅拌器加以溶解混合， 即可调制得彩色 滤光片用感光性树脂组合物， 具体组分见表 3。
比较例的方法同实施例 11 , 具体组分见表 3 , 其中， 比较例 1所用的寡 聚物为季戊四醇四丙烯酸酯， 比较例 2所用的寡聚物为双季戊四醇六丙烯酸 酯， 比较例 3所用的寡聚物为丙氧化三羟曱基丙烷三丙烯酸酯。 评价方式
1.耐碱性： 将感光性树脂层， 以 400-700nm波长光测其透过率， 然后于 2% NaOH中放置 5分钟后， 再以 400-700nm波长光测其透过率， 根据其光 透过率变化比例以如下基准评价。
o: 透过率变化 5%以下
Δ: 透过率变化 5-10%
： 透过率变化 10%以上
2. 残渣： 旋涂感光性树脂至 3um, 在 90°C下预烘 3min, 以紫外光照射， 之后浸渍于 23°C显影液中 2min显影， 未曝光部分除去后， 以纯水洗净， 再 以 200°C后烘 40min, 即可形成所要的感光性树脂图案， 以电子显微镜观察， 确定表面是否有残渣存在。
o: 无残渣
Δ: 少许残渣
X 较多残渣
3.表面平整性； 按如上第 2方法制得指定感光性树脂图案， 用扫描电镜 观察其表面是否平整。
Δ: 少许裂纹
： 坑洼不平整
具体见检测结果见表 3。
表 3: 实施例与比较例及其评价结果 编号
成份（重量份） 实施例 比较例
4 5 6 7 1 2 3 碱溶性树脂 A 100 100 100 100 100 100 100
B-1 80 100
B-2 100
可聚合寡聚物 B-3 80
B-4 80 100
B-5 100 光引发剂 C 50 50 50 50 50 50 50 颜料 D 200 200 200 200 200 200 200 有机溶剂 E 800 800 800 800 800 800 800
耐碱性 o o o o o Δ o 评价项目 残渣 o o o o Δ o
表面 o o Δ o o
结论： 由表 2结果可见， 本发明实施例的负性光刻胶树脂组合物的耐碱 性、 表面残渣留存性、 表面平整性均优于比较例。 实验例 15-19 负性光刻胶树脂组合物
表 4: 实施例 15-19负性光刻胶树脂组合物的评价结果
Figure imgf000011_0001
结论： 由表 4可见， 本发明实施例的含有所述光敏性寡聚物的负性光刻胶 组合物在制成光刻胶涂布液， 曝光及显像后， 图案边界整齐、 表面平整。 虽然， 上文中已经用一般性说明及具体实施方案对本发明作了详尽的描 述， 但在本发明基础上， 可以对之作一些修改或改进， 这对本领域技术人员 而言是显而易见的。 因此， 在不偏离本发明精神的基础上所做的这些修改或 改进， 均属于本发明要求保护的范围。

Claims

权利要求书
1. 一种光刻胶用光敏性寡聚物， 所述光敏性寡聚物含有不饱和双键基团 和柔性基团， 其中合成所述光敏性寡聚物的单体或化合物为含有不饱和双键 的有机酸类单体、 含有不饱和双键的有机酯类单体、 含有不饱和双键的有机 酰氯类单体 /乙烯类单体、 含有不饱和双键的醇类化合物和含有柔性基团的硅 烷类 /醚类化合物。
2. 根据权利要求 1所述的光刻胶用光敏性寡聚物， 其中所述光敏性寡聚 物重均分子量为 500-5000。
3. 根据权利要求 1所述的光刻胶用光敏性寡聚物， 其中
合成所述光敏性寡聚物的单体或化合物原料的重量份数为：
含有不饱和双键的有机酸类单体 15-35份；
含有不饱和双键的有机酯类单体 10-20份；
含有不饱和双键的有机酰氯类单体 /乙烯类单体 50-80份；
含有不饱和双键的醇类化合物 10-20份； 和 含有柔性基团的硅烷类 /醚类化合物 3-20份。
4. 根据权利要求 1-3任一项所述的光刻胶用光敏性寡聚物， 其中所述含 有不饱和双键的有机酸类单体为选自丙烯酸、 曱基丙烯酸、 巴豆酸、 肉桂酸、 异肉桂酸和 α-曱基肉桂酸中的一种或几种。
5. 根据权利要求 1-3任一项所述的光刻胶用光敏性寡聚物， 其中所述含 有不饱和双键的有机酯类单体为选自丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙酯、 丙烯酸丁酯、 丙烯酸异戊酯、 曱基丙烯酸曱酯、 曱基丙烯酸乙酯、 曱基丙烯 酸丙酯、 曱基丙烯酸丁酯和曱基丙烯酸异丁酯中的一种或几种。
6. 根据权利要求 1-3任一项所述的光刻胶用光敏性寡聚物， 其中所述含 有不饱和双键的有机酰氯类单体 /乙烯类单体为选自苯乙烯、 丁二烯、 乙基丙 烯酰氯和丙烯酰氯或异丁基丙烯酰氯中的一种或几种。
7. 根据权利要求 1-3任一项所述的光刻胶用光敏性寡聚物， 其中所述含 有不饱和双键的醇类化合物为选自烯丙醇、 二戊烯三醇、 三乙烯二醇、 丙烯 酸羟乙酯、 曱基丙烯酸羟乙酯、 丙烯酸羟丙酯和曱基丙烯酸羟丙酯中的一种 或几种。
8. 根据权利要求 1-3任一项所述的光刻胶用光敏性寡聚物， 其中所述含 有柔性基团的硅烷类为选自 (Ν,Ν-二苯乙基 丙基)三曱 硅烷、 1,3-双 (三曱代曱硅烷基)脲、 3-(3-氨基苯氧基)丙基三曱氧基硅烷、 3-½苯丙基三乙 甲硅烷、 3-½苯丙基三甲氧基硅烷、 3-½丙基苯甲基二乙 硅烷、 Ν,Ν-二 (3-氯 -2-羟基苯丙基) 丙基三乙 甲硅烷、 Ν,Ν-二甲 氯代二苯 基硅烷、 三 (二甲 tt)硅烷、 三己基叠氮基硅烷和二 (三甲氧基甲硅烷基丙基) 胺中一种或几种。
9. 根据权利要求 1-3任一项所述的光刻胶用光敏性寡聚物， 其中所述醚 类化合物为选自乙二醇一甲醚乙酸酯和二甘醇二甲醚或二丙婦基乙二醇甲基 醚中的一种或几种。
10. 制备权利要求 1-9任意一项所述的光刻胶用光敏性寡聚物的方法， 包 括：
1 )在 50-80°C、 聚合引发剂存在下， 先将含有不饱和双键的有机酸类单 体、 含有不饱和双键的有机酯类单体、 含有不饱和双键的有机酰氯类单体 /乙 烯类单体进行聚合反应 4-7小时； 和
2 ) 然后加入阻聚剂， 降温至 40-60 °C , 再加入含有不饱和双键的醇类化 合物及含有柔性基团的硅烷类 /醚类化合物进行反应。
11. 一种负性光刻胶组合物， 包含如权利要求 1-9任意一项所述光敏性寡 聚物。
12. 根据权利要求 11所述的负性光刻胶组合物， 包括如下重量份的组分： 碱溶性树脂 5-14.5份
光敏性寡聚物 4- 10份；
光引发剂 1-5.5份;
有机溶剂 30-70份:
颜料 5-20份。
13. 权利要求 11或 12所述负性光刻胶树脂组合物在制备彩色滤光片中 的应用。
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