WO2013139157A1 - 封框胶组合物、防止液晶污染的方法、液晶面板及显示装置 - Google Patents

封框胶组合物、防止液晶污染的方法、液晶面板及显示装置 Download PDF

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Publication number
WO2013139157A1
WO2013139157A1 PCT/CN2012/087102 CN2012087102W WO2013139157A1 WO 2013139157 A1 WO2013139157 A1 WO 2013139157A1 CN 2012087102 W CN2012087102 W CN 2012087102W WO 2013139157 A1 WO2013139157 A1 WO 2013139157A1
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Prior art keywords
liquid crystal
weight
ultraviolet
monomer
sealant
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PCT/CN2012/087102
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English (en)
French (fr)
Inventor
郭仁炜
陈东
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北京京东方光电科技有限公司
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Application filed by 北京京东方光电科技有限公司 filed Critical 北京京东方光电科技有限公司
Priority to JP2015500747A priority Critical patent/JP6188781B2/ja
Priority to KR1020137019186A priority patent/KR101530467B1/ko
Priority to US13/995,318 priority patent/US9644109B2/en
Priority to EP12852440.2A priority patent/EP2829584B1/en
Publication of WO2013139157A1 publication Critical patent/WO2013139157A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of 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
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or 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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • G02F1/1339—Gaskets; Spacers; Sealing of cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/202—LCD, i.e. liquid crystal displays
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1062—UV-curable materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625—Polyacrylic esters or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer
    • C09K2323/059—Unsaturated aliphatic polymer, e.g. vinyl

Definitions

  • Frame sealant composition method for preventing liquid crystal contamination, liquid crystal panel and display device
  • the invention relates to a design of a sealant in a liquid crystal display, a liquid crystal display device and a method for preventing liquid crystal contamination by using a frame sealant, and relates to the use of the sealant.
  • the liquid crystal substrate and the array substrate are filled with liquid crystal, and the periphery is sealed with glue, and the glue is a frame sealant.
  • frame sealants mainly include ultraviolet double bond polymerizable monomers, thermal polymerization monomers, photoinitiators, thermal curing agents and particulate additives.
  • the commonly used frame sealant is crosslinked by a stepwise polymerization method.
  • ultraviolet polymerization is carried out, wherein the photoinitiator generates a radical by ultraviolet light irradiation, and the radical-initiated chain polymerization of the ultraviolet double bond polymerizable monomer to form a polymer, in the process, due to the thermal polymerization monomer
  • the polymerization rate is slower, and the ultraviolet double-bond polymerizable monomer has a faster polymerization rate. Therefore, the high molecular polymer formed by the polymerization of the ultraviolet double bond polymerizable monomer can anchor the thermal polymerization monomer in the sealant and hinder the thermal polymerization.
  • the monomer diffuses into the liquid crystal to prevent the liquid crystal from being contaminated by the sealant, thereby avoiding yellowing and unevenness around the liquid crystal panel.
  • thermal polymerization is further carried out, in which the thermal polymerization monomer is polymerized to form a polymer having excellent mechanical properties, thereby effectively bonding the color filter substrate and the array substrate.
  • the high molecular polymer formed by the polymerization of the ultraviolet double bond polymerizable monomer by the photoinitiator is mostly chain-shaped, and the thermal polymerization monomer cannot be effectively anchored, and there are still few Part of the thermally polymerized monomer diffuses into the liquid crystal, causing contamination of the liquid crystal.
  • the main object of the present invention is to provide a frame sealant composition, a method and a use for preventing liquid crystal contamination by using the frame sealant, a liquid crystal panel and a display device, and a polymerizable oligomer in the sealant and the sealant.
  • the polymer of the ultraviolet double bond polymerizable monomer forms a network polymer in the ultraviolet polymerization reaction, and enhances the anchoring effect of the polymer on the surrounding unreacted thermopolymerizable monomer, thereby reducing the contamination of the liquid crystal by the sealant.
  • an aspect of the invention provides a frame sealant composition comprising an ultraviolet double bond polymerizable monomer and a polymerizable oligomer.
  • the polymerizable oligomer is preferably polyethylene glycol diacrylate or a derivative thereof.
  • the ultraviolet double bond polymerizable monomer is an acrylate, preferably decyl acrylate, decyl decyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate.
  • a frame sealant composition comprising or consisting of the following components:
  • UV double bond polymerizable monomer 20-30 parts by weight
  • Thermal polymerization monomer 15-20 parts by weight
  • Polymerizable oligomer 5-20 parts by weight
  • Photoinitiator 0.1-5 parts by weight
  • Heat curing agent 10-20 parts by weight
  • Granular additive 0-20 parts by weight
  • the polymerizable oligomer is polyethylene glycol diacrylate or a derivative thereof.
  • polyethylene glycol diacrylate and derivatives thereof have a weight average molecular weight of from 200 to 3,000.
  • polyethylene glycol diacrylate and derivatives thereof have a weight average molecular weight of from 200 to 1,000.
  • the ultraviolet double bond polymerizable monomer is decyl acrylate, decyl methacrylate, ethyl acrylate, propyl acrylate or butyl acrylate;
  • the thermal polymerization monomer is an epoxy group thermal polymerization monomer
  • the photoinitiator is dibenzoyl peroxide, dodecyl peroxide, azobisisobutyronitrile, azobisisoheptanenitrile, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate. ;
  • the heat curing agent is a curing agent;
  • the particulate additive is silica particles.
  • epoxy group thermal polymerization monomer is ethylene glycol diglycidyl ether
  • the amino curing agent is 1,8-diamino-3,6-dioxaoctane.
  • the present invention further provides a method of preventing liquid crystal contamination by using a frame sealant composition, the method comprising the steps of:
  • step b) applying the mixture obtained in the step a) to the color filter substrate or / and the array substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • step d) heating the liquid crystal display panel obtained in the step c) to thermally polymerize the thermally polymerizable monomer in the sealant.
  • step a) is protected from light defoaming for 1-5 hours.
  • the ultraviolet light has a wavelength of 350-380 nm, the ultraviolet light irradiation time is l-60 min, and the ultraviolet light irradiation intensity is 0.1-100 mW/cm2.
  • the temperature of the thermal polymerization in the step d) is 50-150 ° C, and the reaction time is 0.5-5 h.
  • the present invention further provides a liquid crystal panel which is sealed with a sealant composition as described above.
  • the present invention further provides a display device comprising the liquid crystal panel as described above.
  • the present invention also provides the use of the above sealant composition for preventing liquid crystal contamination.
  • the frame sealant of the present invention mainly has the following advantages: 1.
  • the sealant of the present invention contains a polymerizable oligomer, and the polymerizable oligomer itself has a chain shape and can be combined with ultraviolet light.
  • the polymer of the bond polymerizable monomer firstly forms a network polymer in the ultraviolet polymerization process, compared with the chain polymer produced by the prior art frame sealant in the ultraviolet polymerization process, the network of the present invention
  • the high molecular polymer is more advantageous for strengthening the anchoring effect of the polymer on the surrounding unreacted thermopolymerizable monomer, and effectively reducing the contamination of the liquid crystal by the sealant; 2.
  • the polymerizable oligomerization in the sealant of the present invention The material itself is a polymer, the molecular weight is large, the molecular structure is linear, and the viscosity is large, and the thermal polymerization monomer, the ultraviolet double bond polymerizable monomer and other components in the sealant can be anchored to some extent before the polymerization reaction occurs. Small score Further, the thermal polymerization monomer, the ultraviolet double bond polymerizable monomer and other small molecules in the sealant are further diffused into the liquid crystal, thereby further reducing the contamination of the liquid crystal by the sealant, and avoiding yellowing and unevenness around the liquid crystal panel. phenomenon. DRAWINGS
  • FIG. 2 is a SEM photograph of a network polymer produced by reacting a polymerizable oligomer in a frame sealant with a polymer of an ultraviolet double bond polymerizable monomer;
  • FIG. 3 is a schematic view showing the diffusion of unreacted monomers into the liquid crystal before and after the addition of the polymerizable oligomer in the frame sealant of the present invention
  • FIG. 4 is a flow chart of a method for preventing liquid crystal contamination by using a frame sealant according to the present invention
  • Fig. 6 is a FT-IR spectrum of the liquid crystal sealed by a sealant after the sealant of the polymerizable oligomer is added to the liquid crystal display according to the embodiment of the present invention.
  • the central idea of the present invention is to further add a polymerizable oligomer to the seal component of the existing liquid crystal display, so that the polymerizable oligomer and the ultraviolet double bond polymerizable monomer are first formed into a network in the ultraviolet polymerization process.
  • the molecular polymer utilizes the network structure of the network polymer to effectively anchor the surrounding thermal polymerization monomer, thereby reducing the contamination of the liquid crystal by the sealant, and at the same time, the polymerizable oligomer itself is an oligomer, The surrounding unreacted monomer is anchored to some extent before the polymerization reaction, thereby further reducing the contamination of the liquid crystal by the sealing 411 gel.
  • the frame sealant composition of the present invention contains an ultraviolet double bond polymerizable monomer and a polymerizable oligomer.
  • the polymerizable oligomer is preferably polyethylene glycol diacrylate or a derivative thereof.
  • the ultraviolet double bond polymerizable monomer may be an acrylate.
  • decyl acrylate, decyl methacrylate, ethyl acrylate, propyl acrylate or butyl acrylate are more preferable.
  • the ultraviolet double bond polymerizable monomer generally refers to a class of compounds which contain a double bond and which polymerize under the conditions initiated by the photoinitiator.
  • the sealant composition of the present invention comprises or consists of the following components: UV double bond polymerizable monomer: 20-30 parts by weight;
  • Thermal polymerization monomer 15-20 parts by weight
  • Polymerizable oligomer 5-20 parts by weight
  • Photoinitiator 0.1-5 parts by weight
  • Thermal curing agent 10-20 parts by weight
  • Granular additive 0-20 parts by weight.
  • the molecular weight generally means a weight average molecular weight unless otherwise specified.
  • the ultraviolet double bond polymerizable monomer in the frame sealant composition of the present invention may be an acrylate, preferably decyl acrylate, decyl decyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate;
  • the monomer is preferably an epoxy-based thermopolymerizable monomer, particularly preferably ethylene glycol diglycidyl ether;
  • the photoinitiator is preferably dibenzoyl peroxide, dodecanoyl peroxide, azobisisobutyronitrile And azobisisoheptanenitrile, diisopropyl peroxydicarbonate or dicyclohexyl peroxydicarbonate;
  • the thermosetting agent is preferably an amino curing agent, particularly preferably 1,8-diamino-3. 6-dioxaoctane or the like;
  • the particulate additive may be silica particles or the like.
  • Figure 1 is a schematic view showing the reaction principle between components in the frame sealant of the present invention.
  • the polymer of the ultraviolet double bond polymerizable monomer in Fig. 1 is schematically illustrated as a poly(decyl acrylate). For the convenience of describing the reaction, only one unit of polyacrylic acid acrylate is shown to be reacted to form a polymer network polymer.
  • Photoinitiator 12 is excited by ultraviolet light to generate The free radicals 121 and 122, the polymer of the ultraviolet double bond polymerizable monomer 13 are reacted with a polymerizable oligomer and a polymer of an uninitiated ultraviolet double bond polymerizable monomer to form a network polymer.
  • the polymerizable oligomer may also be reacted with a polymer of an ultraviolet double bond polymerizable monomer after radical initiation, or a polymerizable monomer may be polymerized with a UV double bond after the radical polymerization
  • the polymer and the uninitiated polymerizable oligomer react to form a network polymer 14 .
  • SEM scanning electron microscope
  • the polymerizable oligomer in the frame sealant of the present invention is a polymer
  • the molecular weight is large, for example, the molecular weight of PEGDA 1000 is 1000, the molecular structure is linear, the viscosity is large, and the gel can be anchored in the sealant before polymerization.
  • the small molecule is advantageous for further reducing the diffusion of unreacted ultraviolet polymerizable monomer and thermally polymerized monomer or other small molecules in the sealant during the polymerization into the liquid crystal.
  • the polymerizable monomer and the thermally polymerizable monomer or other small molecule are small molecules which are easily diffused into the liquid crystal 1 to cause contamination of the liquid crystal near the edge 4 of the glass substrate.
  • the polymerizable oligomer is a polymer, and the molecular weight is large (for example, PEGDA 1000 has a molecular weight of 1000), the molecular structure is linear, the viscosity is large, and the polymer can be anchored before polymerization.
  • the small molecules in the sealant are further beneficial to reduce the diffusion of small molecular substances in the sealant into the liquid crystal during the polymerization process, thereby reducing the contamination of the liquid crystal by the sealant.
  • the content of the polymerizable oligomer in the frame sealant of the invention affects the effect of controlling liquid crystal pollution.
  • the content of the polymerizable oligomer is low, the polymer network formed after the ultraviolet polymerization is sparse, and the anchoring effect on the small molecule is small. It is weaker; when the content of polymerizable oligomer is higher, the polymer network formed after ultraviolet polymerization is denser, and the anchoring effect on small molecular substances in the sealant is stronger, so that the smaller the molecular substance is less likely to diffuse into the liquid crystal. Therefore, it is more advantageous to reduce the contamination of the liquid crystal by the sealant.
  • the content of the polymerizable oligomer is increased, the content of other substances in the sealant (such as the thermal polymerization monomer, the heat curing agent) is lowered, and the sealant is applied between the upper and lower substrates (the Array substrate and the CF substrate).
  • the adhesion is weakened, thereby affecting the performance of the liquid crystal display panel. Therefore, only when the polymerizable oligomer in the sealant is kept at an appropriate level, it is advantageous to reduce the contamination of the liquid crystal by the sealant without affecting the performance of the liquid crystal display panel.
  • the content of the polymerizable oligomer in the frame sealant of the present invention is an optimum content range determined on the basis of comprehensive consideration of various factors.
  • the molecular weight of the polymerizable oligomer also affects the effect of controlling liquid crystal contamination.
  • the content of the polymerizable oligomer and the number of double bonds are the same, when the molecular weight of the polymerizable oligomer is small, the number of moles is increased.
  • the molar number of the double bond functional group is correspondingly increased, and the polymerization reaction is more likely to occur during the polymerization to form a polymer network, thereby facilitating anchoring of small molecular substances around, but the smaller molecular weight polymerizable oligomer is in the mixing process.
  • the polymerizable oligomer of the present invention preferably has a weight average molecular weight of from 200 to 3,000, more preferably from 200 to 1,000.
  • the present invention further provides the use of the above-mentioned frame sealant composition preventing liquid
  • the method of crystal contamination for example, mainly includes the following steps, as shown in FIG. 4:
  • step a) mixing the frame sealant composition as described above, and performing light-proof defoaming treatment for 1-5 hours; b) uniformly applying the mixture obtained in step a) to the color filter substrate or/and the array substrate, Then filling the color filter substrate and the array substrate with a liquid crystal and a box to obtain a liquid crystal display panel;
  • the ultraviolet double-bond polymerizable monomer is polymerized to form a polymer after ultraviolet light irradiation, and then the polymerizable oligomer in the sealant is polymerizable with the ultraviolet double bond.
  • the monomer polymer undergoes ultraviolet polymerization, wherein the ultraviolet light has a wavelength of 350-380 nm, the ultraviolet light irradiation time is l-60 min, and the ultraviolet light irradiation intensity is 0.1-100 mW/cm 2 ;
  • step d) heating the liquid crystal display panel obtained in the step c) to thermally polymerize the thermally polymerized monomer in the sealant, wherein the temperature of the thermal polymerization is 50-150 ° C, and the reaction time is 0.5-5 h.
  • the sealant composition used in the method is the same as the components of the above-mentioned frame sealant composition of the present invention, and will not be described herein.
  • the present invention further provides a liquid crystal panel which is sealed with the frame sealant composition of the present invention.
  • the present invention further provides a display device comprising a liquid crystal panel which is sealed with the frame sealant composition of the present invention.
  • the present invention further provides the use of the frame sealant composition of the present invention in preventing contamination of a liquid crystal panel.
  • Example 1 Preparation of frame sealant 1 and use of sealant 1 to prevent liquid crystal contamination
  • a) 20 parts by weight of an ultraviolet double bond polymerizable monomer (ethyl acrylate), 15 parts by weight of a thermally polymerizable monomer (ethylene glycol diglycidyl acid), and 7 parts by weight of a polymerizable oligomer (polyethyl b) Diol diacrylate, containing 2 C C double bonds, weight average molecular weight 2500), 0.1 part by weight of photoinitiator (dibenzoyl peroxide) and 10 parts by weight of heat curing agent (1,8-II) Mixing amino-3,6-dioxaoctane to obtain a homogeneous mixture, and placing the above mixture in a defoamer for light defoaming treatment for 1 h;
  • an ultraviolet double bond polymerizable monomer ethyl acrylate
  • a thermally polymerizable monomer ethylene glycol diglycidyl acid
  • a polymerizable oligomer polyethyl
  • step b) uniformly coating the mixture obtained in step a) onto the color filter substrate, and then arranging the color filter substrate with the array
  • the column substrate is filled with liquid crystal and the box is obtained to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 350 nm, the ultraviolet light irradiation time is 1 min, and the ultraviolet light irradiation intensity is 100 mW/cm 2 ;
  • a) 21 parts by weight of an ultraviolet double bond polymerizable monomer (decyl acrylate), 16.5 parts by weight of a thermally polymerizable monomer (ethylene glycol diglycidyl acid), and 5 parts by weight of a polymerizable oligomer (polyethyl b) Diol diacrylate, containing 2 C C double bonds, weight average molecular weight 3000), 0.5 parts by weight of photoinitiator (dodecyl peroxide), 12 parts by weight of heat curing agent (1,8-diamino group) -3,6-dioxaoctane), and 2 parts by weight of the particulate additive (silica) are mixed to obtain a homogeneous mixture, and the mixture is placed in a defoamer for light-resistant defoaming treatment for 1.5 hours;
  • an ultraviolet double bond polymerizable monomer decyl acrylate
  • 16.5 parts by weight of a thermally polymerizable monomer
  • step b) uniformly applying the mixture obtained in the step a) to the color filter substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 370 nm, the ultraviolet light irradiation time is 5 min, and the ultraviolet light irradiation intensity is 95 mW/cm 2 ;
  • a) 23 parts by weight of an ultraviolet double bond polymerizable monomer (decyl methacrylate), 15 parts by weight of a thermally polymerizable monomer (ethylene glycol diglycidyl acid), and 10 parts by weight of a polymerizable oligomer (Polethylene glycol diacrylate, containing 2 C C double bonds, weight average molecular weight 2000), 1 part by weight of photoinitiator (azobisisobutyronitrile), 13 parts by weight of heat curing agent (1,8) - dioxooctane), and 5 parts by weight of the particulate additive (silica) are mixed to obtain a homogeneous mixture, and the mixture is placed in a defoamer for light defoaming treatment for 2 hours;
  • an ultraviolet double bond polymerizable monomer decyl methacrylate
  • a thermally polymerizable monomer ethylene glycol diglycidyl acid
  • a polymerizable oligomer Polyethylene glycol diacrylate,
  • step b) uniformly coating the mixture obtained in the step a) onto the array substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • irradiating the liquid crystal display panel with ultraviolet light wherein the wavelength of the ultraviolet light is 375 nm, The irradiation time of ultraviolet light is lOmin, and the irradiation intensity of ultraviolet light is 80mW/cm 2 ;
  • a) 22 parts by weight of an ultraviolet double bond polymerizable monomer (propyl acrylate), 17 parts by weight of a thermally polymerizable monomer (ethylene glycol diglycidyl acid), and 12 parts by weight of a polymerizable oligomer (polyethyl b) ⁇ diol diacrylate ⁇ contains 2 C C double bonds, weight average molecular weight 1500), 1.5 parts by weight of photoinitiator (azobisisoheptanenitrile), 15 parts by weight of heat curing agent (1,8-two Amino-3,6-dioxaoctane), and 7 parts by weight of a particulate additive (silica) are mixed to obtain a homogeneous mixture, and the mixture is placed in a defoamer for light-free defoaming treatment for 3 hours;
  • an ultraviolet double bond polymerizable monomer propyl acrylate
  • 17 parts by weight of a thermally polymerizable monomer ethylene glycol diglycid
  • step b) uniformly coating the mixture obtained in the step a) onto the array substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 365 nm, the ultraviolet light irradiation time is 40 min, and the ultraviolet light irradiation intensity is 35 mW/cm 2 ;
  • a) 25 parts by weight of an ultraviolet double bond polymerizable monomer (propyl acrylate), 17.5 parts by weight of a thermally polymerizable monomer (ethylene glycol diglycidyl acid), 15 parts by weight of a polymerizable oligomer (polyethyl b) ⁇ diol diacrylate ⁇ contains 2 C C double bonds, weight average molecular weight 1000), 2 parts by weight of photoinitiator (diisopropyl peroxydicarbonate), 17 parts by weight of heat curing agent (1,8) -dioxaoctane), and 10 parts by weight of the particulate additive (silica) are mixed to obtain a homogeneous mixture, and the mixture is placed in a defoamer for light-free defoaming treatment for 3.5 hours;
  • step b) uniformly applying the mixture obtained in the step a) to the color filter substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 360 nm, the ultraviolet light irradiation time is 50 min, and the ultraviolet light irradiation intensity is 15 mW/cm 2 ;
  • step b) uniformly applying the mixture obtained in the step a) to the color filter substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 365 nm, the ultraviolet light irradiation time is 20 min, and the ultraviolet light irradiation intensity is 65 mW/cm 2 ;
  • a) 30 parts by weight of an ultraviolet double bond polymerizable monomer (butyl acrylate), 18 parts by weight of a thermally polymerizable monomer (ethylene glycol diglycidyl acid), and 19 parts by weight of a polymerizable oligomer (polyethyl b) Diol diacrylate, containing 2 C C double bonds, weight average molecular weight 400), 4 parts by weight of photoinitiator (dodecyl peroxide), 19 parts by weight of heat curing agent (1,8-diamino group) -3,6-dioxaoctane), and 20 parts by weight of a particulate additive (silica) are mixed to obtain a homogeneous mixture, and the mixture is placed in a defoamer for light-free defoaming treatment for 4.5 hours;
  • a particulate additive silicon
  • step b) uniformly applying the mixture obtained in the step a) to the color filter substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 355 nm, the ultraviolet light irradiation time is 60 min, and the ultraviolet light irradiation intensity is O.lmW/cm 2 ;
  • Example 8 Preparation of sealant 8 and prevention of liquid crystal contamination by using sealant 8 a) 29 parts by weight of a UV double bond polymerizable monomer (butyl acrylate), 20 parts by weight of a thermally polymerizable monomer (Ethylene acrylate) Alcohol diglycidyl acid), 20 parts by weight of a polymerizable oligomer (polyethylene glycol diacrylate, containing 2 CC double bonds, weight average molecular weight of 200), 5 parts by weight of a photoinitiator (azo diiso) 20 parts by weight of a heat curing agent (1,8-diamino-3,6-dioxaoctane), and 17 parts by weight of a particulate additive (silica) to obtain a UV double bond polymerizable monomer (butyl acrylate), 20 parts by weight of a thermally polymerizable monomer (Ethylene acrylate) Alcohol diglycidyl acid), 20 parts by weight of a polymerizable
  • step b) uniformly applying the mixture obtained in the step a) to the color filter substrate and the array substrate, and then filling the color filter substrate and the array substrate with the liquid crystal and the box to obtain a liquid crystal display panel;
  • the ultraviolet light has a wavelength of 380 nm, the ultraviolet light irradiation time is 30 min, and the ultraviolet light irradiation intensity is 50 mW/cm 2 ;
  • step d) heating the liquid crystal display panel obtained in the step c) to thermally polymerize the thermally polymerized monomer in the sealant, wherein the temperature of the thermal polymerization is 150 ° C and the reaction time is 0.5 h.
  • the comparative sealant in the comparative example was the same as Example 5 except that the polymerizable oligomer was not contained in the sealant.
  • the liquid crystal display panel was sealed with the same sealant without the polymerizable oligomer in the same manner as in the above examples.
  • liquid crystal pollution test ⁇ Using a Fourier transform infrared spectrometer FT-IR (Perkin Elmer, room temperature test) for the liquid crystal in the vicinity of the sealant of the liquid crystal display panel of Examples 1, 3, 4, 5, 7, and 8, respectively, and the liquid crystal display panel obtained in the comparative example The liquid crystal near the sealant was tested to compare the characteristic absorption peak intensity of the epoxy group of the thermally polymerizable monomer at the position of ⁇ 1 .
  • FIG. 5 is a view showing that a frame sealant (curve 0') in which a polymerizable oligomer is added in Example 5 of the present invention and a control sealant (curve 0) in which a polymerizable oligomer is not added are respectively applied to a liquid crystal display, and the liquid crystal is subjected to liquid crystal display. Comparative FT-IR spectrum of frame sealant contamination, as can be seen from Fig.
  • a liquid crystal display panel sealed with a control sealant which does not contain a polymerizable oligomer, and a seal comprising a polymerizable oligomer of the present invention The liquid crystal display panel of the frame-sealed liquid crystal display panel has a characteristic absorption peak intensity of the thermally polymerized monomer epoxy group at the position of 916 cm- 1 , that is, the residual thermal polymerization monomer in the liquid crystal is less.
  • 6 is an FT-IR spectrum of the liquid crystal frame sealant after the frame sealant of the polymerizable oligomer of the present invention is applied to the liquid crystal display, respectively, in the first, third, fourth, seventh, and eighth embodiments of the present invention (curves 1-5).
  • the liquid crystal of the liquid crystal display panel sealed with the sealant of the first, third, fourth, seventh, and eighth embodiments of the present invention is 916 cm-
  • the characteristic absorption peak intensity of the thermopolymerizable monomer epoxy group at the 1 position is weak (the FT-IR patterns of Examples 2 and 6 are similar to the FT-IR patterns of Examples 1, 3, 4, 7, and 8, 916 cm).
  • the characteristic absorption peak intensity of the thermopolymerizable monomer epoxy group at the 1- position is weak.
  • the present invention only exemplifies the FT-IR spectrum corresponding to Examples 1, 3, 4, 5, 7, and 8), and the above indicates that Sealing the liquid crystal display panel with the sealant comprising the polymerizable oligomer of the invention can effectively prevent the unreacted thermal polymerization monomer in the sealant from diffusing into the liquid crystal, thereby effectively reducing the contamination of the liquid crystal by the sealant and avoiding the liquid crystal Yellowing and unevenness appear around the panel.

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Abstract

一种封框胶组合物、液晶显示设备及利用封框胶组合物防止液晶污染的方法，该封框胶组合物由20-30重量份的紫外双键可聚合单体、15-20重量份的热聚合单体、5-20重量份的可聚合低聚物、0.1-5重量份的光引发剂、10-20重量份的热固化剂及0-20重量份的颗粒添加剂组成，其中所述可聚合低聚物为聚乙二醇二丙烯酸酯或其衍生物。通过可聚合低聚物与紫外双键可聚合单体的聚合物之间进行反应生成网状高分子聚合物，有效地增强了聚合物对周围未反应的热聚合单体的锚定作用，从而减少了封框胶对液晶的污染。

Description

封框胶组合物、 防止液晶污染的方法、 液晶面板及显示装置 技术领域
本发明涉及液晶显示器中封框胶的设计、 液晶显示设备及利用封框胶防 止液晶污染的方法， 还涉及该封框胶的用途。 背景技术
在液晶显示面板的制作过程中， 将彩膜 (CF)基板和阵列 (Array)基板对盒 后， 在彩膜基板和阵列基板之间填充液晶， 周边用胶密封， 这种胶即封框胶。 常用的封框胶主要包含紫外双键可聚合单体、 热聚合单体、 光引发剂、 热固 化剂及颗粒添加剂等。
常用的封框胶通过分步聚合的方法进行交联。 首先进行紫外聚合， 该过 程通过紫外光辐照使光引发剂生成自由基， 自由基引发紫外双键可聚合单体 发生链式聚合， 生成高分子聚合物， 该过程中， 由于热聚合单体聚合反应速 度较慢， 紫外双键可聚合单体聚合速度较快， 因此由紫外双键可聚合单体聚 合生成的高分子聚合物便可锚定封框胶中热聚合单体， 阻碍热聚合单体向液 晶中扩散， 防止液晶被封框胶所污染， 从而避免液晶面板周边出现黄变和不 均等现象。 在紫外聚合反应结束后， 再进行热聚合反应， 该过程中热聚合单 体发生聚合， 生成力学性能优良的高分子聚合物， 从而有效粘结彩膜基板和 阵列基板。
以下文献中介绍了通过聚合物网络锚定周围小分子的研究：
[l]Guo JB, Sun J, Zhang LP, Li KX, Cao H, Yang H, Zhu SQ, Polym Advan Technol, 2008: 19: 1504-1512.
[2]Guo JB, Sun J, Li KX, Cao H, Yang H. Liq Cryst, 2008: 35: 87-97.
[3]Guo RW, Cao H, Yang CY, Wu XJ, Meng QY, Liu T, He WL, Cheng ZK Yang H. Liq Cryst, 2010: 37: 311-316.
目前， 现有的封框胶在紫外聚合过程中， 紫外双键可聚合单体通过光引 发剂聚合生成的高分子聚合物多为链状， 不能有效地锚定热聚合单体， 仍有 少部分热聚合单体扩散进入液晶， 对液晶造成污染。 发明内容
有鉴于此， 本发明的主要目的在于提供一种封框胶组合物、 利用该封框 胶防止液晶污染的方法和用途、 液晶面板及显示装置， 通过封框胶中的可聚 合低聚物与紫外双键可聚合单体的聚合物在紫外聚合反应中生成网状高分子 聚合物， 增强聚合物对周围未反应的热聚合单体的锚定作用， 从而减少封框 胶对液晶的污染。
为了达到上述目的， 本发明的一个方面提供一种封框胶组合物， 该封框 胶组合物含有紫外双键可聚合单体和可聚合低聚物。 其中， 所述可聚合低聚 物优选为为聚乙二醇二丙烯酸酯或其衍生物。 进一步优选地， 紫外双键可聚 合单体为丙烯酸酯， 优选为丙烯酸曱酯、 曱基丙烯酸曱酯、 丙烯酸乙酯、 丙 烯酸丙酯或丙烯酸丁酯。
在本发明的另一个方面提供了一种该封框胶组合物， 该封框胶组合物包 括以下组分或者由以下组分组成：
紫外双键可聚合单体， 20-30重量份；
热聚合单体， 15-20重量份；
可聚合低聚物， 5-20重量份；
光引发剂， 0.1-5重量份;
热固化剂， 10-20重量份；
颗粒添加剂， 0-20重量份；
其中， 所述可聚合低聚物为聚乙二醇二丙烯酸酯或其衍生物。
进一步地， 所述聚乙二醇二丙烯酸酯及其衍生物的重均分子量为 200-3000。
进一步地， 所述聚乙二醇二丙烯酸酯及其衍生物的重均分子量为 200-1000。
进一步地， 所述紫外双键可聚合单体为丙烯酸曱酯、 曱基丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙酯或丙烯酸丁酯；
所述热聚合单体为环氧基热聚合单体；
所述光引发剂为过氧化二苯曱酰、 过氧化十二酰、 偶氮二异丁腈、 偶氮 二异庚腈、 过氧化二碳酸二异丙酯或过氧化二碳酸二环己酯；
所述热固化剂为 固化剂； 所述颗粒添加剂为二氧化硅颗粒。
进一步地， 所述环氧基热聚合单体为乙二醇二缩水甘油醚；
所述氨基固化剂为 1,8-二氨基 -3,6-二氧杂辛烷。
本发明进一步提供一种利用封框胶组合物防止液晶污染的方法， 该方法 包含以下步骤：
a)将如上所述的封框胶组合物混合并进行避光脱泡处理；
b)将步骤 a)得到的混合物涂覆到彩膜基板或 /和阵列基板上， 然后将彩膜 基板与阵列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 使封框胶中的可聚合低聚物与 紫外双键可聚合单体的聚合物发生紫外聚合反应；
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应。
进一步地， 所述步骤 a)中避光脱泡处理 1-5个小时。
进一步地， 所述步骤 c)中紫外光的波长为 350-380nm, 紫外光辐照时间 为 l-60min, 紫外光辐照强度为 0.1-100mW/cm2。
进一步地， 所述步骤 d)中热聚合反应的温度为 50-150°C , 反应时间为 0.5-5h。
本发明进一步提供一种液晶面板， 所述液晶面板釆用如上所述的封框胶 组合物进行密封。
本发明进一步提供一种显示装置， 所述显示装置包括如上所述的液晶面 板。
本发明还提供上述封框胶组合物在防止液晶污染中的用途。
与现有技术相比， 本发明的封框胶主要有以下优点： 一、 本发明的封框 胶中含有可聚合低聚物， 这种可聚合低聚物自身呈链状， 可与紫外双键可聚 合单体的聚合物首先在紫外聚合过程中生成网状高分子聚合物， 与现有技术 的封框胶在紫外聚合过程中生成的链状高分子聚合物相比， 本发明的网状高 分子聚合物更有利于加强聚合物对周围未反应的热聚合单体的锚定作用， 有 效地减少了封框胶对液晶的污染； 二、 本发明封框胶中的可聚合低聚物本身 为聚合物， 分子量较大， 分子结构呈线性， 且粘度较大， 可在发生聚合反应 前一定程度地锚定封框胶中的热聚合单体、 紫外双键可聚合单体及其他小分 子， 进一步减少封框胶中热聚合单体、 紫外双键可聚合单体及其他小分子向 液晶中扩散， 从而进一步减少封框胶对液晶的污染， 避免液晶面板周边出现 黄变和不均等现象。 附图说明
为了更清楚地说明本发明实施例的技术方案， 下面将对实施例的附图作 简单地介绍，显而易见地，下面描述中的附图仅仅涉及本发明的一些实施例， 而非对本发明的限制。
图 1为本发明封框胶中各组分之间的反应原理示意图；
图 2为本发明封框胶中可聚合低聚物与紫外双键可聚合单体的聚合物发 生反应生成的网状高分子聚合物的 SEM照片；
图 3为本发明封框胶添加可聚合低聚物前后未反应的单体向液晶中扩散 的示意图；
图 4为本发明利用封框胶防止液晶污染的方法流程图；
图 5为将本发明实施例中添加可聚合低聚物的封框胶与未添加可聚合低 聚物的封框胶分别应用于液晶显示器后液晶受封框胶污染的对比 FT-IR 图 谱；
图 6为将本发明实施例中添加可聚合低聚物的封框胶密封液晶显示器后 液晶受封框胶污染的 FT-IR图谱。
附图标记说明
1 液晶
2 未聚合的单体
3 封框胶
4 玻璃基板边缘
5 可聚合低聚物
12光引发剂
121、 122 自由基
13紫外双键可聚合单体的聚合物
14高分子聚合物 具体实施方式
为使本发明实施例的目的、 技术方案和优点更加清楚， 下面将结合本发 明实施例的附图，对本发明实施例的技术方案进行清楚、 完整地描述。显然， 所描述的实施例是本发明的一部分实施例， 而不是全部的实施例。 基于所描 述的本发明的实施例， 本领域普通技术人员在无需创造性劳动的前提下所获 得的所有其他实施例， 都属于本发明保护的范围。
本发明的中心思想在于： 在现有的液晶显示器封框胶成分中进一步加入 可聚合低聚物， 使可聚合低聚物与紫外双键可聚合单体首先在紫外聚合过程 中生成网状高分子聚合物， 利用网状高分子聚合物的网状结构有效地锚定周 围的热聚合单体， 从而减少封框胶对液晶的污染， 同时可聚合低聚物本身为 低聚物， 可在聚合反应前一定程度地锚定周围未反应的单体， 从而进一步减 少封 411胶对液晶的污染。
在一个实施方案中。 本发明的封框胶组合物含有紫外双键可聚合单体和 可聚合低聚物。 其中， 所述可聚合低聚物优选为为聚乙二醇二丙烯酸酯或其 衍生物。 进一步优选地， 紫外双键可聚合单体可为丙烯酸酯。 其中更优选丙 烯酸曱酯、 曱基丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙酯或丙烯酸丁酯。
所述紫外双键可聚合单体一般是指含有双键的并且在光引发剂引发的条 件下能发生聚合的一类化合物。
在一个实施方案中， 本发明的封框胶组合物包含或者由以下组分组成： 紫外双键可聚合单体： 20-30重量份；
热聚合单体： 15-20重量份；
可聚合低聚物： 5-20重量份；
光引发剂： 0.1-5重量份;
热固化剂： 10-20重量份；
颗粒添加剂： 0-20重量份。
其中所述可聚合低聚物优选为聚乙二醇二丙烯酸酯或其衍生物 , 所述聚 乙二醇二丙烯酸酯 (PEGDA)及其衍生物中可含 2-4个 C=C双键 (本发明中涉 及的 C=C双键指聚乙二醇二丙烯酸酯主链上的 C=C双键)，优选含 2个 C=C 双键， 重均分子量可为 200-3000, 优选 200-1000, 如分子量为 200(PEGDA 200)、 400(PEGDA 400)、 600(PEGDA 600)或 1000(PEGDA 1000)。 在本文中， 如果没有特别指明， 分子量一般指重均分子量。
本发明的封框胶组合物中的紫外双键可聚合单体可为丙烯酸酯， 优选为 丙烯酸曱酯、 曱基丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙酯或丙烯酸丁酯； 所 述热聚合单体优选为环氧基热聚合单体,特别优选可为乙二醇二缩水甘油醚； 所述光引发剂优选为过氧化二苯曱酰、 过氧化十二酰、 偶氮二异丁腈、 偶氮 二异庚腈、 过氧化二碳酸二异丙酯或过氧化二碳酸二环己酯等； 所述热固化 剂优选为氨基固化剂， 特别优选为 1,8-二氨基 -3,6-二氧杂辛烷等； 所述颗粒 添加剂可为二氧化硅颗粒等。
图 1为本发明封框胶中各组分之间的反应原理示意图。 本发明封框胶中 的可聚合低聚物 (聚乙二醇二丙烯酸酯) 5含有两个 C=C双键， 可在紫外聚合 反应过程中与紫外双键可聚合单体的聚合物 (图 1 中的紫外双键可聚合单体 的聚合物示意为聚丙烯酸曱酯， 为便于描述反应， 图中仅示出了聚丙烯酸曱 酯的 1个单元)反应生成高分子网状聚合物。如图 1所示 (图中 Υ、 Ζ代表碳链 衍生物， X、 Yi , M、 N和 n均表示重复单元的数量)， 具体的反应路径如下： 光引发剂 12受紫外光激发， 生成自由基 121和 122, 紫外双键可聚合单体的 聚合物 13 经自由基引发后与可聚合低聚物及未被引发的紫外双键可聚合单 体的聚合物反应生成网状高分子聚合物 14 , 另外， 可聚合低聚物也可经自由 基引发后与紫外双键可聚合单体的聚合物反应， 或可聚合低聚物经自由基引 发后与紫外双键可聚合单体的聚合物及未被引发的可聚合低聚物反应生成网 状高分子聚合物 14。
图 2为本发明封框胶中可聚合低聚物与紫外双键可聚合单体的聚合物反 应生成的网状高分子聚合物的扫描电子显微镜 (SEM , Leicas 440)照片 (WD=27mm,放大 5000倍)，从图 2可知， 该网状高分子聚合物呈网状结构， 对小分子物质具有较好的锚定作用， 可有效地阻止未反应的热聚合单体向液 晶中扩散， 从而减少封框胶对液晶的污染。
另外， 由于本发明封框胶中的可聚合低聚物属聚合物， 分子量较大， 如 PEGDA 1000分子量为 1000, 分子结构呈线性， 粘度较大， 能锚定聚合反应 前封框胶中的小分子， 有利于进一步减少在聚合过程中封框胶中未反应的紫 外可聚合单体和热聚合单体或其他小分子向液晶中扩散。 如图 3所示， 未添 加可聚合低聚物 5之前， 由于封框胶 3中未聚合的单体 2(包括未反应的紫外 可聚合单体和热聚合单体或其他小分子， 主要为热聚合单体)是小分子， 易向 液晶 1中扩散， 对玻璃基板边缘 4附近的液晶造成污染。 而在封框胶中添加 可聚合低聚物后， 由于可聚合低聚物属聚合物， 分子量较大 (如 PEGDA 1000 分子量为 1000), 分子结构呈线性， 粘度较大， 能够锚定聚合前封框胶中的 小分子， 进一步有利于减少在聚合过程中封框胶中的小分子物质向液晶中扩 散， 从而减少封框胶对液晶的污染。
本发明封框胶中可聚合低聚物的含量会影响到控制液晶污染的效果， 可 聚合低聚物含量较低时， 紫外聚合后生成的高分子网络较稀疏， 对小分子的 锚定作用较弱； 而当可聚合低聚物含量较高时， 紫外聚合后生成的高分子网 络较密， 对封框胶中小分子物质的锚定作用较强， 使小分子物质越不容易扩 散进入液晶， 从而更有利于减少封框胶对液晶的污染。 但当可聚合低聚物含 量增加时， 封框胶中其他物质 (如热聚合单体、 热固化剂）的含量就会降低， 使封框胶对上下基板 (Array基板和 CF基板)之间的粘结力减弱， 从而对液晶 显示面板的性能产生影响。 因此， 只有当封框胶中可聚合低聚物保持适当含 量时， 才有利于减少封框胶对液晶的污染， 同时又不影响液晶显示面板的性 能。 本发明封框胶中可聚合低聚物的含量即是在综合考虑各种因素的基础上 确定的最佳含量范围。
另外， 可聚合低聚物的分子量也会影响到控制液晶污染的效果， 在可聚 合低聚物的含量及双键个数相同的情况下， 可聚合低聚物的分子量较小时， 摩尔数增加， 含有的双键官能团摩尔数相应增加， 在聚合过程中越容易发生 聚合反应生成高分子网络， 从而越有利于锚定周围的小分子物质， 但较小分 子量的可聚合低聚物在混合过程中容易与其它小分子化合物搅拌均匀， 从而 使可聚合低聚物本身对周围小分子物质的锚定作用减弱； 而当可聚合低聚物 的分子量较大时， 摩尔数较少， 含有的双键官能团摩尔数相应较少， 在聚合 过程中越不易发生聚合反应生成高分子网络， 从而不利于锚定周围的小分子 物质， 但由于高分子量的可聚合低聚物分子链较长， 使其本身对周围小分子 物质的锚定作用增强， 从而有利于阻止周围小分子物质向液晶中扩散。 因此 实际中需要选择适宜分子量的可聚合低聚物， 以达到较好控制液晶污染的效 果， 本发明优选可聚合低聚物的重均分子量为 200-3000, 更优选 200-1000。
在一个实施方案中， 本发明进一步提供了利用上述封框胶组合物防止液 晶污染的方法， 例如， 主要包含以下步骤， 如图 4所示：
a)将如上所述的封框胶组合物混合， 并进行避光脱泡处理 1-5个小时； b)将步骤 a)得到的混合物均匀涂覆到彩膜基板或 /和阵列基板上， 然后将 彩膜基板与阵列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 紫外双键可聚合单体经紫外光 辐照后发生聚合生成聚合物， 然后使封框胶中的可聚合低聚物与紫外双键可 聚合单体的聚合物发生紫外聚合反应， 其中紫外光的波长为 350-380nm, 紫 外光辐照时间为 l-60min, 紫外光辐照强度为 0.1-100mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 50-150°C , 反应时间为 0.5-5h。
该方法中用到的封框胶组合物与上述本发明封框胶组合物中各组分相 同， 在此不再赘述。
本发明进一步提供一种液晶面板， 所述液晶面板釆用本发明的封框胶组 合物进行密封。
本发明进一步提供一种显示装置， 包括液晶面板， 所述液晶面板釆用本 发明的封框胶组合物进行密封。
本发明进一步提供了本发明的封框胶组合物在防止液晶面板污染中的用 途。
以下为本发明封框胶及利用该封框胶防止液晶污染的具体实施例 (本发 明实施例中用到的化学物品均可通过市售获得， 例如从 Aldrich公司购买获 得)。 一、 封框胶的制备及防止液晶污染的方法
实施例 1 : 封框胶 1的制备以及利用封框胶 1防止液晶污染
a)将 20重量份的紫外双键可聚合单体 (丙烯酸乙酯)、 15重量份的热聚合 单体 (乙二醇二缩水甘油酸)、 7重量份的可聚合低聚物 (聚乙二醇二丙烯酸酯， 含 2个 C=C双键， 重均分子量 2500)、 0.1重量份的光引发剂 (过氧化二苯曱 酰)及 10重量份的热固化剂（1,8-二氨基 -3,6-二氧杂辛烷)混合， 得到均匀的混 合物,并将上述混合物放入脱泡器中进行避光脱泡处理 lh;
b)将步骤 a)得到的混合物均匀涂覆到彩膜基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 350nm, 紫外光辐照时间为 lmin, 紫外光辐照强度为 100mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 50 °C , 反应时间为 5h。 实施例 2: 封框胶 2的制备以及利用封框胶 3防止液晶污染
a)将 21重量份的紫外双键可聚合单体 (丙烯酸曱酯)、 16.5重量份的热聚 合单体 (乙二醇二缩水甘油酸)、 5 重量份的可聚合低聚物 (聚乙二醇二丙烯酸 酯， 含 2个 C=C双键， 重均分子量 3000)、 0.5重量份的光引发剂 (过氧化十 二酰)、 12重量份的热固化剂（1,8-二氨基 -3,6-二氧杂辛烷)、 及 2重量份的颗 粒添加剂 (二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入脱泡器 中进行避光脱泡处理 1.5h;
b)将步骤 a)得到的混合物均匀涂覆到彩膜基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 370nm, 紫外光辐照时间为 5min, 紫外光辐照强度为 95mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 60 °C , 反应时间为 4.5h。 实施例 3: 封框胶 3的制备以及利用封框胶 3防止液晶污染
a)将 23重量份的紫外双键可聚合单体 (曱基丙烯酸曱酯)、 15重量份的热 聚合单体（乙二醇二缩水甘油酸)、 10重量份的可聚合低聚物 (聚乙二醇二丙烯 酸酯， 含 2个 C=C双键， 重均分子量 2000)、 1重量份的光引发剂 (偶氮二异 丁腈)、 13重量份的热固化剂（1,8-二 二氧杂辛烷)、 及 5重量份的颗 粒添加剂 (二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入脱泡器 中进行避光脱泡处理 2h;
b)将步骤 a)得到的混合物均匀涂覆到阵列基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 375nm, 紫外光辐照时间为 lOmin, 紫外光辐照强度为 80mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 75 °C , 反应时间为 3h。 实施例 4: 封框胶 4的制备以及利用封框胶 4防止液晶污染
a)将 22重量份的紫外双键可聚合单体 (丙烯酸丙酯)、 17重量份的热聚合 单体（乙二醇二缩水甘油酸)、 12 重量份的可聚合低聚物 (聚乙二醇二丙烯酸 酉^ 含 2个 C=C双键， 重均分子量 1500)、 1.5重量份的光引发剂 (偶氮二异 庚腈)、 15重量份的热固化剂（1,8-二氨基 -3,6-二氧杂辛烷)、 及 7重量份的颗 粒添加剂（二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入脱泡器 中进行避光脱泡处理 3h;
b)将步骤 a)得到的混合物均匀涂覆到阵列基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 365nm, 紫外光辐照时间为 40min, 紫外光辐照强度为 35mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 90 °C , 反应时间为 2.7h。 实施例 5: 封框胶 5的制备以及利用封框胶 5防止液晶污染
a)将 25重量份的紫外双键可聚合单体 (丙烯酸丙酯)、 17.5重量份的热聚 合单体 (乙二醇二缩水甘油酸)、 15重量份的可聚合低聚物 (聚乙二醇二丙烯酸 酉^ 含 2个 C=C双键， 重均分子量 1000)、 2重量份的光引发剂 (过氧化二碳 酸二异丙酯)、 17重量份的热固化剂（1,8-二 二氧杂辛烷)、 及 10重量 份的颗粒添加剂 (二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入 脱泡器中进行避光脱泡处理 3.5h;
b)将步骤 a)得到的混合物均匀涂覆到彩膜基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 360nm, 紫外光辐照时间为 50min, 紫外光辐照强度为 15mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 100 °C , 反应时间为 2.5h。 实施例 6: 封框胶 6的制备以及利用封框胶 6防止液晶污染
a)将 27重量份的紫外双键可聚合单体 (丙烯酸乙酯)、 19重量份的热聚合 单体（乙二醇二缩水甘油酸)、 17 重量份的可聚合低聚物 (聚乙二醇二丙烯酸 酉^ 含 2个 C-C双键， 重均分子量 600)、 3重量份的光引发剂 (过氧化二碳酸 二环己酯)、 18重量份的热固化剂（1,8-二氨基 -3,6-二氧杂辛烷)、 及 15重量份 的颗粒添加剂（二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入脱 泡器中进行避光脱泡处理 4h;
b)将步骤 a)得到的混合物均匀涂覆到彩膜基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 365nm, 紫外光辐照时间为 20min, 紫外光辐照强度为 65mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 110°C , 反应时间为 2h。 实施例 7: 封框胶 7的制备以及利用封框胶 7防止液晶污染
a)将 30重量份的紫外双键可聚合单体 (丙烯酸丁酯)、 18重量份的热聚合 单体（乙二醇二缩水甘油酸)、 19 重量份的可聚合低聚物 (聚乙二醇二丙烯酸 酯， 含 2个 C=C双键， 重均分子量 400)、 4重量份的光引发剂（过氧化十二 酰)、 19重量份的热固化剂（1,8-二氨基 -3,6-二氧杂辛烷)、 及 20重量份的颗粒 添加剂 (二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入脱泡器中 进行避光脱泡处理 4.5h;
b)将步骤 a)得到的混合物均匀涂覆到彩膜基板上， 然后将彩膜基板与阵 列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 355nm, 紫外光辐照时间为 60min, 紫外光辐照强度为 O.lmW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 130°C , 反应时间为 lh。 实施例 8: 封框胶 8的制备以及利用封框胶 8防止液晶污染 a)将 29重量份的紫外双键可聚合单体 (丙烯酸丁酯)、 20重量份的热聚合 单体（乙二醇二缩水甘油酸)、 20 重量份的可聚合低聚物 (聚乙二醇二丙烯酸 酯，含 2个 C-C双键，重均分子量 200)、 5重量份的光引发剂 (偶氮二异庚腈)、 20重量份的热固化剂（1,8-二氨基 -3,6-二氧杂辛烷)、 及 17重量份的颗粒添加 剂 (二氧化硅)混合， 得到均匀的混合物， 并将上述混合物放入脱泡器中进行 避光脱泡处理 5h;
b)将步骤 a)得到的混合物均匀涂覆到彩膜基板和阵列基板上， 然后将彩 膜基板与阵列基板填充液晶并对盒， 得到液晶显示面板；
c)利用紫外光对液晶显示面板进行辐照， 其中紫外光的波长为 380nm, 紫外光辐照时间为 30min, 紫外光辐照强度为 50mW/cm2;
d)对步骤 c)中得到的液晶显示面板加热， 使封框胶中的热聚合单体发生 热聚合反应， 其中热聚合反应的温度为 150°C , 反应时间为 0.5h。
Figure imgf000014_0001
二、 比较例
比较例中的对照封框胶除封框胶中不包含可聚合低聚物外， 其余均与实 施例 5相同。 并按照与上述实施例相同的方法步骤， 釆用该不含有可聚合低 聚物的对照封框胶密封液晶显示面板。 三、 液晶污染测试 釆用傅立叶变换红外光谱仪 FT-IR ( Perkin Elmer , 室温测试 )分别对实 施例 1、 3、 4、 5、 7、 8中液晶显示面板封框胶附近的液晶及比较例中得到的 液晶显示面板封框胶附近的液晶进行测试， 对比 ^όαη·1位置上热聚合单体 环氧基的特征吸收峰强度。
图 5为将本发明实施例 5中添加可聚合低聚物的封框胶（曲线 0' )与未 添加可聚合低聚物的对照封框胶（曲线 0 )分别应用于液晶显示器后液晶受 封框胶污染的对比 FT-IR图谱， 由图 5可知， 相对于釆用不包含可聚合低聚 物的对照封框胶密封的液晶显示面板， 釆用本发明包含可聚合低聚物的封框 胶密封的液晶显示面板的液晶在 916cm-1位置上热聚合单体环氧基的特征吸 收峰强度较弱， 即液晶中残留的热聚合单体较少。 图 6为分别将本发明实施 例 1、 3、 4、 7、 8中添加可聚合低聚物的封框胶应用于液晶显示器后液晶受 封框胶污染的 FT-IR图谱（曲线 1-5分别对应实施例 1、 3、 4、 7、 8 ) , 从 图中看出， 釆用本发明实施例 1、 3、 4、 7、 8的封框胶密封的液晶显示面板 的液晶在 916cm-1位置上热聚合单体环氧基的特征吸收峰强度较弱（实施例 2 和 6的 FT-IR图语与实施例 1、 3、 4、 7、 8的 FT-IR图语相似， 916cm-1位置 上热聚合单体环氧基的特征吸收峰强度较弱， 本发明仅以实施例 1、 3、 4、 5、 7、 8对应的 FT-IR图谱为例说明）， 以上表明釆用本发明包含可聚合低聚物 的封框胶密封液晶显示面板可有效阻止封框胶中未反应的热聚合单体向液晶 中扩散， 从而有效地减少封框胶对液晶的污染， 避免液晶面板周边出现黄变 和不均等现象。
以上所述仅是本发明的示范性实施方式， 而非用于限制本发明的保护范 围， 本发明的保护范围由所附的权利要求确定。

Claims

权 利 要 求 书
1、一种封框胶组合物， 其含有紫外双键可聚合单体和可聚合低聚物， 其 中， 所述可聚合低聚物为聚乙二醇二丙烯酸酯或其衍生物。
2、如权利要求 1所述的封框胶组合物， 其中， 所述紫外双键可聚合单体 为丙烯酸酯， 优选为丙烯酸曱酯、 曱基丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙 酯或丙烯酸丁酯。
3、 一种封框胶组合物， 其中， 包括以下组分或由以下组分组成： 紫外双键可聚合单体， 20-30重量份；
热聚合单体， 15-20重量份；
可聚合低聚物， 5-20重量份；
光引发剂， 0.1-5重量份;
热固化剂， 10-20重量份；
颗粒添加剂， 0-20重量份；
其中， 所述可聚合低聚物为聚乙二醇二丙烯酸酯或其衍生物。
4、如权利要求 3所述的封框胶组合物 , 其中， 所述聚乙二醇二丙烯酸酯 及其衍生物的重均分子量为 200-3000。
5、如权利要求 4所述的封框胶组合物 , 其中， 所述聚乙二醇二丙烯酸酯 及其衍生物的重均分子量为 200-1000。
6、如权利要求 3所述的封框胶组合物， 其中， 所述紫外双键可聚合单体 为丙烯酸酯， 优选为丙烯酸曱酯、 曱基丙烯酸曱酯、 丙烯酸乙酯、 丙烯酸丙 酯或丙烯酸丁酯；
所述热聚合单体为环氧基热聚合单体；
所述光引发剂为过氧化二苯曱酰、 过氧化十二酰、 偶氮二异丁腈、 偶氮 二异庚腈、 过氧化二碳酸二异丙酯或过氧化二碳酸二环己酯；
所述热固化剂为 固化剂；
所述颗粒添加剂为二氧化硅颗粒。
7、如权利要求 6所述的封框胶组合物， 其中， 所述环氧基热聚合单体为 乙二醇二缩水甘油醚； 所述氨基固化剂为 1,8-二氨基 -3,6-二氧杂辛烷。
8、 一种利用封框胶组合物防止液晶污染的方法， 其中， 包含以下步骤： a )将如权利要求 1-7中任一项所述的封框胶组合物混合并进行避光脱泡 处理；
b )将步骤 a )得到的混合物涂覆到彩膜基板或 /和阵列基板上， 然后将彩 膜基板与阵列基板填充液晶并对盒， 得到液晶显示面板；
c )利用紫外光对液晶显示面板进行辐照，使封框胶中的可聚合低聚物与 紫外双键可聚合单体的聚合物发生紫外聚合反应；
d )对步骤 C )中得到的液晶显示面板加热， 使封框胶中的热聚合单体发 生热聚合反应。
9、 如权利要求 8所述的方法， 其中， 所述步骤 a ) 中避光脱泡处理 1-5 个小时。
10、 如权利要求 8所述的方法， 其中， 所述步骤 c ) 中紫外光的波长为 350-380nm,紫外光辐照时间为 l-60min,紫外光辐照强度为 0.1-100mW/cm2。
11、 如权利要求 8所述的方法， 其中， 所述步骤 d ) 中热聚合反应的温 度为 50-150°C , 反应时间为 0.5-5h。
12、 一种液晶面板， 其中， 所述液晶面板釆用如权利要求 1-7中任一项 所述的封框胶组合物进行密封。
13、 一种显示装置， 其中， 所述显示装置包括如权利要求 12所述的液晶 面板。
14、 权利要求 1-7中任一项所述的封框胶组合物在防止液晶污染中的用 途。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI510603B (zh) * 2014-12-19 2015-12-01 Au Optronics Corp 框膠材料以及顯示裝置

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102654980B (zh) 2012-01-09 2015-01-14 京东方科技集团股份有限公司 电子纸显示器件及驱动方法
CN102702987B (zh) 2012-03-21 2015-02-18 北京京东方光电科技有限公司 封框胶组合物、防止液晶污染方法、液晶面板及显示装置
CN103064208B (zh) * 2013-01-23 2015-06-10 深圳市华星光电技术有限公司 一种聚合物稳定垂直配向液晶显示面板及液晶显示器
CN103087641A (zh) * 2013-01-23 2013-05-08 深圳市华星光电技术有限公司 一种边框胶材、液晶显示面板以及相应的液晶显示器
CN103980832B (zh) * 2014-04-17 2018-04-06 京东方科技集团股份有限公司 一种封框胶、显示面板的封装方法及显示面板
CN103992749B (zh) * 2014-05-04 2016-05-25 京东方科技集团股份有限公司 一种封框胶及其制备方法，液晶显示面板
KR101863011B1 (ko) * 2014-10-30 2018-05-31 미쓰이 가가쿠 가부시키가이샤 액정 표시 패널의 제조 방법, 액정 표시 패널, 및 액정 시일제 조성물
CN108770358A (zh) 2015-12-31 2018-11-06 聚合物胶粘剂密封胶系统公司 用于具有密度改性剂的柔性密封剂的系统和方法
KR102463384B1 (ko) 2016-02-19 2022-11-04 애버리 데니슨 코포레이션 접착제를 제조하는 2단계 방법 및 관련 조성물
EP3532520A1 (en) 2016-10-25 2019-09-04 Avery Dennison Corporation Block polymers with photoinitiator groups in backbone and their use in adhesive compositions
CN106336818B (zh) * 2016-11-08 2019-12-17 深圳市华星光电技术有限公司 框胶及其制备方法与窄边框液晶显示装置
CN106398557A (zh) * 2016-11-21 2017-02-15 深圳市华星光电技术有限公司 边框胶
CN107068896B (zh) 2016-12-28 2019-06-18 上海天马有机发光显示技术有限公司 一种有机发光显示面板及其制备方法
CN108003273B (zh) * 2017-12-14 2020-12-01 合肥鑫晟光电科技有限公司 pH响应型聚合物及其制备方法以及光刻胶组合物
JP6916949B2 (ja) * 2018-02-14 2021-08-11 富士フイルム株式会社 光学フィルム、偏光板、画像表示装置
CN109280494A (zh) * 2018-10-11 2019-01-29 深圳市华星光电技术有限公司 封框胶、封框胶的光固化方法以及液晶显示装置
CN111363392B (zh) * 2020-04-08 2021-09-24 Tcl华星光电技术有限公司 框胶、显示面板及其制备方法
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CN114231200A (zh) * 2022-02-24 2022-03-25 宁波惠之星新材料科技有限公司 一种保护膜及其制备方法和使用方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62129376A (ja) * 1985-12-02 1987-06-11 Toagosei Chem Ind Co Ltd 漏水管の補修方法
CN101343527A (zh) * 2007-07-10 2009-01-14 赢创罗姆有限责任公司 可溶胀的聚合物用于密封的用途
CN101838505A (zh) * 2009-10-26 2010-09-22 东莞市派乐玛新材料技术开发有限公司 一种金属按键填字粘接密封的有色光固化胶粘剂及其制备方法
CN102702987A (zh) * 2012-03-21 2012-10-03 北京京东方光电科技有限公司 封框胶组合物、防止液晶污染方法、液晶面板及显示装置

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0762123B2 (ja) * 1985-01-08 1995-07-05 武田薬品工業株式会社 接着方法
JPS6116257A (ja) 1984-06-30 1986-01-24 Mazda Motor Corp エンジンの排気還流制御装置
JP3597597B2 (ja) * 1994-06-08 2004-12-08 株式会社日本触媒 吸水性樹脂及びその製造方法
DE19632749A1 (de) * 1996-08-14 1998-02-19 Hoechst Ag Härtungskomponente für Epoxidharze und deren Verwendung
KR100906926B1 (ko) * 2001-05-16 2009-07-10 세키스이가가쿠 고교가부시키가이샤 경화성 수지 조성물, 표시 소자용 시일제 및 표시 소자용주입구 밀봉제
WO2004027502A1 (ja) * 2002-09-19 2004-04-01 Mitsui Chemicals, Inc. 液晶シール剤組成物及びそれを用いた液晶表示パネルの製造方法
US6833176B2 (en) 2003-01-06 2004-12-21 General Electric Company Radiation curable microstructure-bearing articles
JP4385736B2 (ja) * 2003-02-10 2009-12-16 Ｄｉｃ株式会社 紫外線硬化型組成物及びそれを用いた光ディスク
JP2004339341A (ja) * 2003-05-15 2004-12-02 Shin Etsu Chem Co Ltd シール剤組成物
TW200508314A (en) * 2003-06-04 2005-03-01 Sekisui Chemical Co Ltd A liquid crystal display device and curing resin composition, sealing material for the same
CN1290953C (zh) * 2003-07-01 2006-12-20 中国乐凯胶片集团公司 一种用于偏光片保护膜层压的uv光固化胶粘剂
TW200636032A (en) * 2005-04-13 2006-10-16 Lg Chemical Ltd Acrylic adhesive composition having excellent impact resistance, optical film using the adhesive composition, and liquid crystal display comprising the optical film
CN102050930B (zh) * 2005-12-27 2012-07-25 三井化学株式会社 含蒽醌衍生物的光固化性树脂组合物
CN101564551B (zh) * 2009-06-05 2012-07-25 北京科技大学 一种丙烯酸酯类形状记忆性人工晶状体材料及制备方法
CN102321233B (zh) * 2011-06-23 2013-04-24 北京科技大学 一种环氧树脂基聚合物分散液晶薄膜材料的制备方法
JP6116257B2 (ja) 2013-01-22 2017-04-19 矢崎総業株式会社 ヘッドアップディスプレイ装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62129376A (ja) * 1985-12-02 1987-06-11 Toagosei Chem Ind Co Ltd 漏水管の補修方法
CN101343527A (zh) * 2007-07-10 2009-01-14 赢创罗姆有限责任公司 可溶胀的聚合物用于密封的用途
CN101838505A (zh) * 2009-10-26 2010-09-22 东莞市派乐玛新材料技术开发有限公司 一种金属按键填字粘接密封的有色光固化胶粘剂及其制备方法
CN102702987A (zh) * 2012-03-21 2012-10-03 北京京东方光电科技有限公司 封框胶组合物、防止液晶污染方法、液晶面板及显示装置

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
GUO JB; SUN J; LI KX; CAO H; YANG H., LIQ CRYST, vol. 35, 2008, pages 87 - 97
GUO JB; SUN J; ZHANG LP; LI KX; CAO H; YANG H; ZHU SQ, POLYM ADVAN TECHNOL, vol. 19, 2008, pages 1504 - 1512
GUO RW; CAO H; YANG CY; WU XJ; MENG QY; LIU T; HE WL; CHENG ZH; YANG H, LIQ CRYST, vol. 37, 2010, pages 311 - 316
See also references of EP2829584A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI510603B (zh) * 2014-12-19 2015-12-01 Au Optronics Corp 框膠材料以及顯示裝置

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