WO2018213695A1 - Curable compositions for one drop sealant applications - Google Patents

Curable compositions for one drop sealant applications Download PDF

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Publication number
WO2018213695A1
WO2018213695A1 PCT/US2018/033371 US2018033371W WO2018213695A1 WO 2018213695 A1 WO2018213695 A1 WO 2018213695A1 US 2018033371 W US2018033371 W US 2018033371W WO 2018213695 A1 WO2018213695 A1 WO 2018213695A1
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group
linear
branched
agents
resin
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PCT/US2018/033371
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French (fr)
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Laxmisha SRIDHAR
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Henkel IP & Holding GmbH
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Priority to KR1020197037159A priority Critical patent/KR20200008590A/en
Publication of WO2018213695A1 publication Critical patent/WO2018213695A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C07D233/34—Ethylene-urea
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23—Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1483—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C09J171/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes
    • 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

Definitions

  • the present invention relates to resins useful in adhesive and sealant compositions and particularly as one drop fill sealants for liquid crystal applications.
  • the present invention permits assembly of LCD panels without migration of the sealant resin into the liquid crystal or vice versa during LCD assembly and/or curing of the resin.
  • ODF one drop fill
  • a sealant is dispensed on an electrode-equipped substrate to form a frame of a display element, and liquid crystals are dropped inside the depicted frame.
  • another electrode equipped substrate is joined thereto under vacuum.
  • the sealant undergoes a curing process, either by a combination of UV and thermal or by thermal only process.
  • the ODF method has a few problems in that the sealant material in uncured state comes into contact with the liquid crystal ("LC") during the assembly process. This could cause reduction in electro-optical properties of the LC by migration of resin into the LC or vice versa, or ionic impurities. Hence, design of resin systems for sealant material that show good liquid crystal resistance (less contamination) along with good adhesion and moisture barrier properties has remained a challenge.
  • LC liquid crystal
  • the present invention relates to unique resins and ODF compositions made therefrom.
  • Q may be selected from:
  • R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
  • heterocycloarylenes the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
  • heterocycloarylenes can optionally contain O or S or hydroxyl group
  • R 1 is H or methyl
  • X is selected from CH 2 ,
  • n 3 are each independently 0-10;
  • n 2 is 1-10;
  • Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene;
  • Z is a covalent bond linking the aryl group to the oxygen, a carbonyl group, or hydrocarbylene linker group
  • R 2 is a substituent on the aromatic ring selected from alkyl, alkoxy, aryloxy, halide, aliphatic and aromatic groups.
  • Q may be selected from:
  • R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricyeloalkylenes, bicycloalkylarylenes,
  • heterocycloarylenes the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricyeloalkylenes, bicycloalkylarylenes,
  • heterocycloarylenes can optionally contain O or S or hydroxyl group
  • Ri is H or methyl
  • X is selected from CH 2 , m and n 3 are each independently 0-10;
  • n 2 is 1-10;
  • Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene;
  • Z is a covalent bond linking the aryl group to the sulfur, or a hydrocarbylene group; and R 2 is a substituent on the aromatic ring selected from alkyl, alkoxy, aryloxy, halide, aliphatic and aromatic groups.
  • Yi and Y 2 can be same or different and are polymerizable functionalities selected from vinylbenzyl, vinylaryl, (meth)acrylate, allyl, cinnamyl and glycidyl;
  • Xi and X 2 area covalent bonds connecting the Y 1 and Y 2 groups to the nitrogen may be selected from one or more of alkylene or cycloalkylene each of which may optionally contain one or more hetero atoms such as oxygen, sulfur or nitrogen;
  • Ri is a substituent on the cyclic urea ring selected from alkyl, cycloalkyl, aryl, aralkyl;
  • X is a hetero atom selected from O, S, or N; or a functionality selected from ester, urethane, urea, imide, carbonate; or a group selected from alkylene, cycloalkyene, oxyalkylene optionally containing hydroxyl functionality at any position or one or more atoms selected from O, S, N at any position; and
  • R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
  • heterocycloarylenes the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
  • heterocycloarylenes can optionally contain O or S or hydroxyl group; or R may also be silicone or siloxane in combination with one or more of the above-mentioned multivalent linkers.
  • the resins of the present invention are useful in a wide variety of applications including adhesive and sealant.
  • One particularly effective use of the inventive resins is as an ODF sealants for assembling LCD panels.
  • the present invention provides resins (which also includes oligomers and polymers) useful for preparing curable compositions which may be used for ODF sealants.
  • the glycidyl ether/ester compounds useful in synthesizing the inventive hybrid resins described herein is not particularly limited, and examples of the epoxy compounds available in the market include: bisphenol A type epoxy resins such as Epikote 828EL and Epikote 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.); bisphenol F type epoxy resins such as Epikote 806 and Epikote 4004 (all manufactured by Japan Epoxy Resin Co., Ltd.);
  • bisphenol S type epoxy resins such as Epiclon EXA1514 (manufactured by Dainippon Ink and Chemicals Inc.) and SE 650 manufactured by Shin A T&C ; 2,2'-diallyl bisphenol A type epoxy resins such as RE-81 ONM (manufactured by Nippon Kayaku Co., Ltd.); hydrogenated bisphenol type epoxy resins such as Epiclon EXA7015 (manufactured by Dainippon Ink and Chemicals Inc.); propyleneoxide-added bisphenol A type epoxy resins such as EP-4000S (manufactured by ADEKA Corporation); resorcinol type epoxy resins such as EX-201
  • Examples of the commercially available phenol novolak type epoxy compound include Epiclon N-740, N-770, N-775 (all manufactured by Dainippon Ink and Chemicals Inc.), Epikote 152, Epikote 154 (all manufactured by Japan Epoxy Resin Co., Ltd.), and the like.
  • cresol novolak type epoxy compound examples include Epiclon N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP and N-672- EXP (all manufactured by Dainippon Ink and Chemicals Inc.); an example of the commercially available biphenyl novolak type epoxy compound is NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); examples of the commercially available trisphenol novolak type epoxy compound include EP1032S50 and EP1032H60 (all manufactured by Japan Epoxy Resin Co., Ltd.); examples of the commercially available dicyclopentadiene novolak type epoxy compound include XD-1000-L (manufactured by Nippon Kayaku Co., Ltd.) and HP-7200 (manufactured by Dainippon Ink and Chemicals Inc.); examples of the commercially available bisphenol A type epoxy compound include Epikote 828, Epikote 834, Epikote 1001, Epikot
  • Examples of the commercially available bisphenol F type epoxy compound include Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epiclon 830 (manufactured by Dainippon Ink and Chemicals Inc.); an example of the commercially available 2,2'-diallyl bisphenol A type epoxy compound is RE-810NM
  • Examples of the alicyclic epoxy compounds useful in synthesizing the inventive resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring and cyclohexene oxide- or cyclopentene oxide containing compounds obtained by epoxidizing cyclohexene ring or cyclopentene ring-containing compounds.
  • hydro genated bisphenol A diglycidyl ether 3,4-epoxycyclohexylmethyl 3,4- epoxycyclohexanecarboxylate, 3 ,4-epoxy-l-methyl cyclohexyl-3 ,4-epoxy- 1 - methylcyclohexanecarboxylate, 6-methyl-3 ,4-epoxycyclohexylmethyl-6-methyl-3 ,4-epoxy- cyclohexanecarboxylate, 3 ,4-epoxy-3 -methylcyclohexylmethyl 3 ,4-epoxy-3 - methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcylcohexylmethyl-3,4-epoxy-5- methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane- metadiox
  • UVR-6100, UVR-6105, UVR-6110, UVR-6128, and UVR-6200 products of Union Carbide Corporation
  • CELLOXIDE 3000 CYCLMER A200, CYCLMER MIOO, CYCLMER MlOl, EPOLEAD GT- 301, EPOLEAD GT-302, EPOLEAD 401, EPOLEAD 403, ETHB, and EPOLEADHD 300 (from Daicel Chemical Industries, Ltd.); KRM-21 10, and KRM-2199 (from ADEKA
  • ODF sealant compositions may also include a free radical initiator (which may be triggered by exposure to elevated temperature conditions or radiation in the electromagnetic spectrum) and a curing agent.
  • a free radical initiator which may be triggered by exposure to elevated temperature conditions or radiation in the electromagnetic spectrum
  • a curing agent may also be employed.
  • Useful thermal free radical initiators include organic peroxides and azo compounds, examples of which include: azo free radical initiators such as AIBN
  • organic peroxide free radical initiators include dilauroyl peroxide, 2,2-di(4,4-di(tert-butylperoxy)cyclohexyl)propane, di(tert-butylperoxyisopropyl) benzene, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl monoperoxymaleate, 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane, tert-butylperoxy 2-ethylhexyl carbonate, tert-amyl peroxy-2- ethylhexano
  • the thermal free radical initiators with a higher decomposition rate is ordinarily desired, as this can generate free radicals more easily at common cure temperatures (such as in the range of 80 to 130°C) and give faster cure speed, which can reduce the contact time between liquid resin and liquid crystal, and reduce the liquid crystal contamination.
  • common cure temperatures such as in the range of 80 to 130°C
  • the decomposition rate of initiator is too high, the viscosity stability at room temperature will be influenced and thereby reducing the work life of the sealant.
  • a convenient way of expressing the decomposition rate of an initiator at a specified temperature is in terms of its half-life i.e., the time required to decompose one-half of the peroxide originally present.
  • T ⁇ the temperature at which each initiator has a half-life
  • the most reactive (fastest) initiator would be the one with the lowest 10 hour ⁇ ⁇ temperature.
  • the thermal free radical initiator with a 10 hour T] 2 temperature of 30 to 80°C is preferred, and with a 10 hour Ti / 2 temperature of 40-70°C is more preferred.
  • the thermal free radical initiator used in the resin composition is in an amount of usually 0.01 to 3 parts by weight, and preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the inventive resin in the curable composition of the present invention.
  • Useful UV free radical initiators include Norrish type I cleavage photoinitiators that are commercially available from CIBA and BASF. These photoinitiators are used in the amount 0.1-5wt%, more preferably in about 0.2 to 3wt% in the formulation.
  • Examples of useful epoxy curing agent include but are not limited to the Ajicure series of hardeners available from Ajinomoto Fine-Techno Co., Inc,; the Amicure series of curing agents available from Air products and the JERCURETM products available from
  • the curable composition may optionally contain, as desired, a further component capable of a photopolymerization reaction such as a vinyl ether compound.
  • the curable composition may further comprise additives, resin components and the like to improve or modify properties such as flowability, dispensing or printing property, storage property, curing property and physical property after curing.
  • additives may be contained in the composition as desired, for example, organic or inorganic fillers, thixotropic agents, silane coupling agents, diluents, modifiers, coloring agents such as pigments and dyes, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents and the like; however it is not limited to these.
  • the composition preferably comprises an additive selected from the group consisting of organic or inorganic filler, a thixotropic agent, and a silane coupling agent.
  • These additives may be present in amounts of about 0.1% to about 50% by weight of the total composition, more preferably from about 2% to about 10% by weight of the total composition.
  • the filler may include inorganic fillers such as silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulphate, gypsum, calcium silicate, talc, glass bead, sericite activated white earth, bentonite, aluminum nitride, silicon nitride, and the like; meanwhile, organic fillers such as poly(methyl) methacrylate, poly(ethyl) methacrylate, poly(propyl) methacrylate, poly(butyl) methacrylate, butylacrylate-methacrylic acid-(methyl) methacrylate copolymer, polyacrylonitrile, polystyrene, polybutadiene,
  • inorganic fillers such as silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum
  • polypentadiene polyisoprene, polyisopropylene, and the like. These may be used alone or in combination. These fillers may be present in amounts of about 1% to about 80%, more preferably from about 5% to about 30% by weight of the total composition.
  • the thixotropic agent may include, but is not limited to, talc, fume silica, superfine surface-treated calcium carbonate, fine particle alumina, plate-like alumina; layered compounds such as montmorillonite, spicular compounds such as aluminum borate whisker, and the like. Among them, talc, fume silica and fine alumina are particularly desired. These agents may be present in amounts of about 1% to about 50%, more preferably from about 1% to about 30% by weight of the total composition.
  • the silane coupling agent may include, but is not limited to, ⁇ - aminopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ - methacryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxylsilane, and the like.
  • the curable composition according to the present invention may be obtained by mixing the aforementioned each component by means of, for example, a mixer such as a stirrer having stirring blades and a three roll mill.
  • the composition is liquid at ambient with the viscosity of 200-400 Pa.s (at 25°C) at 1.5s-l shear rate.
  • the present invention also relates to a method for manufacturing a liquid crystal display having a liquid crystal layer between a first substrate and a second substrate, by means of a liquid crystal one-drop-filling process.
  • the method comprises the steps of:
  • the first substrate and the second substrate used in the present invention are usually transparent glass substrates.
  • transparent electrodes, active matrix elements (such as TFT), alignment film(s), a color filter and the like are formed on at least one of the opposed faces of the two substrates. These constitutions may be modified according to the type of the LCD.
  • the manufacturing method according to the present invention may be thought to be applied for any type of the LCD.
  • the curable composition is applied on the periphery portion of the surface of the first substrate so as to lap around the substrate circumference in a frame shape.
  • the portion where the curable composition is applied in a frame shape is referred as a seal region.
  • the curable composition can be applied by a known method such as screen printing and dispensing.
  • step (b) the liquid crystal is then dropped onto the center region surrounded by the seal region in the frame shape on the surface of the first substrate.
  • This step is preferably conducted under reduced pressure.
  • step (c) said second substrate is then placed over said first substrate, and
  • the curable composition cures partially and shows the strength at a level that displacement does not occur by handling, whereby the two substrates are temporally fixed.
  • the radiation time is preferably short, for example not longer than 5 minutes, preferably not longer than 3 minutes, more preferably not longer than 1 minute.
  • heating the curable composition allows it to achieve the final curing strength, whereby the two substrates are finally bonded.
  • the thermal curing in the step (e) is generally heated at a temperature of 80 to 130°C, and preferably of 100 to 120°C, with the heating time of 30 minutes to 3 hours, typically 1 hour.
  • the organic layer was washed several times with deionized water and dried over anhydrous Na 2 S0 4 . After filtration, 5g of silica gel and 4g of sillitin were added and stirred for lh. The solids were filtered and washed with 50mL of ethyl acetate. 2000ppm of t-butylcatechol was added and the solvent evaporated to yield the BPA styrenyl epoxy resin as a viscous liquid (32g, 76%).
  • N,N'-(4-Vinylbenzyl)ethylene urea was afforded as a solid (31g, 86%)
  • EP 4088S epoxy resin 36.7g, 118mmol
  • 4-vinylbenzoic acid 37g, 249mmol
  • Hycat 2000S 720mg, 1 wt %)
  • t-butyl catechol 360mg, 5000ppm
  • toluene 78mL
  • 500mL of ethyl acetate was added and the organic layer washed twice with aqueous NaHC0 3 solution (2 x 150mL), twice with 0.1N NaOH solution and several times with deionized water.

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Abstract

The present invention relates to resins useful in adhesive and sealant compositions and particularly as one drop fill sealants for liquid crystal applications. In particular, the present invention permits assembly of LCD panels without migration of the sealant resin into the liquid crystal or vice versa during LCD assembly and/or curing of the resin.

Description

CURABLE COMPOSITIONS FOR ONE DROP SEALANT APPLICATIONS
BACKGROUND
FIELD
[0001] The present invention relates to resins useful in adhesive and sealant compositions and particularly as one drop fill sealants for liquid crystal applications. In particular, the present invention permits assembly of LCD panels without migration of the sealant resin into the liquid crystal or vice versa during LCD assembly and/or curing of the resin.
BRIEF DESCRIPTION OF RELATED TECHNOLOGY
[0002] The one drop fill ("ODF") process is becoming the mainstream process in the assembly of LCD panels in display applications, replacing the conventional vacuum injection technology to meet faster manufacturing process demands. In the ODF process, first, a sealant is dispensed on an electrode-equipped substrate to form a frame of a display element, and liquid crystals are dropped inside the depicted frame. In the next step of the assembly, another electrode equipped substrate is joined thereto under vacuum. Then, the sealant undergoes a curing process, either by a combination of UV and thermal or by thermal only process.
[0003] The ODF method has a few problems in that the sealant material in uncured state comes into contact with the liquid crystal ("LC") during the assembly process. This could cause reduction in electro-optical properties of the LC by migration of resin into the LC or vice versa, or ionic impurities. Hence, design of resin systems for sealant material that show good liquid crystal resistance (less contamination) along with good adhesion and moisture barrier properties has remained a challenge.
[0004] In addition, since typically 5% of excess LC is used than what is required to fill the volume, there is positive pressure of LC on the sealant resin during the vacuum assembly process before the sealant undergoes curing. If the resin is not robust, the LC can penetrate into the sealant during the assembly open time. The resin needs structural characteristics to exhibit sufficient LC resistance to minimize LC contamination or penetration. Typically, polar functionalities, such as hydroxyl, urea, urethane, imide and aromatic groups, are needed for good LC resistance. Hence, design of resin systems for sealant material that show good liquid crystal resistance (less contamination) along with good adhesion and moisture barrier properties has remained a challenge.
[0005] While certain solutions to these issues have been identified in the past (see e.g.,
International Patent Application Nos. PCT/US2016/04611, PCT/CN2015/083966 and
PCT/CN2015/083963), alternative technologies would be desirable for the end user to provide wider choices of potential solutions.
SUMMARY
[0006] The present invention relates to unique resins and ODF compositions made therefrom.
[0007] In one aspect of the invention there is included a resin having the structure I:
I
Figure imgf000003_0001
where Q may be selected from:
Figure imgf000003_0002
R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene or
heterocycloarylenes; the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene and
heterocycloarylenes can optionally contain O or S or hydroxyl group;
R1 is H or methyl;
X is selected from CH2,
Figure imgf000004_0001
m and n3 are each independently 0-10;
n2is 1-10;
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene;
Z is a covalent bond linking the aryl group to the oxygen, a carbonyl group, or hydrocarbylene linker group; and
R2 is a substituent on the aromatic ring selected from alkyl, alkoxy, aryloxy, halide, aliphatic and aromatic groups.
[0008] In still another aspect of the invention there is included a resin having the
S1
Figure imgf000005_0001
where Q may be selected from:
Figure imgf000005_0002
R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricyeloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene or
heterocycloarylenes; the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricyeloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene and
heterocycloarylenes can optionally contain O or S or hydroxyl group;
Ri is H or methyl;
X is selected from CH2,
Figure imgf000006_0001
m and n3 are each independently 0-10;
n2is 1-10;
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene;
Z is a covalent bond linking the aryl group to the sulfur, or a hydrocarbylene group; and R2 is a substituent on the aromatic ring selected from alkyl, alkoxy, aryloxy, halide, aliphatic and aromatic groups.
In still another aspect of the invention there is included a resin having the
III
Figure imgf000006_0002
where Yi and Y2 can be same or different and are polymerizable functionalities selected from vinylbenzyl, vinylaryl, (meth)acrylate, allyl, cinnamyl and glycidyl;
Xi and X2 area covalent bonds connecting the Y1 and Y2 groups to the nitrogen, or may be selected from one or more of alkylene or cycloalkylene each of which may optionally contain one or more hetero atoms such as oxygen, sulfur or nitrogen;
Ri is a substituent on the cyclic urea ring selected from alkyl, cycloalkyl, aryl, aralkyl; and
n = l-10. [0010] In still another aspect of the invention there is included a resin having the structure IV:
IV
Figure imgf000007_0001
where X is a hetero atom selected from O, S, or N; or a functionality selected from ester, urethane, urea, imide, carbonate; or a group selected from alkylene, cycloalkyene, oxyalkylene optionally containing hydroxyl functionality at any position or one or more atoms selected from O, S, N at any position; and
R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene or
heterocycloarylenes; the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene and
heterocycloarylenes can optionally contain O or S or hydroxyl group; or R may also be silicone or siloxane in combination with one or more of the above-mentioned multivalent linkers. DETAILED DESCRIPTION
[0011] The resins of the present invention are useful in a wide variety of applications including adhesive and sealant. One particularly effective use of the inventive resins is as an ODF sealants for assembling LCD panels.
[0012] The present invention provides resins (which also includes oligomers and polymers) useful for preparing curable compositions which may be used for ODF sealants.
[0013] The glycidyl ether/ester compounds useful in synthesizing the inventive hybrid resins described herein is not particularly limited, and examples of the epoxy compounds available in the market include: bisphenol A type epoxy resins such as Epikote 828EL and Epikote 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.); bisphenol F type epoxy resins such as Epikote 806 and Epikote 4004 (all manufactured by Japan Epoxy Resin Co., Ltd.);
bisphenol S type epoxy resins such as Epiclon EXA1514 (manufactured by Dainippon Ink and Chemicals Inc.) and SE 650 manufactured by Shin A T&C ; 2,2'-diallyl bisphenol A type epoxy resins such as RE-81 ONM (manufactured by Nippon Kayaku Co., Ltd.); hydrogenated bisphenol type epoxy resins such as Epiclon EXA7015 (manufactured by Dainippon Ink and Chemicals Inc.); propyleneoxide-added bisphenol A type epoxy resins such as EP-4000S (manufactured by ADEKA Corporation); resorcinol type epoxy resins such as EX-201
(manufactured by Nagase ChemteX Corporation); biphenyl type epoxy resins such as Epikote YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.); sulfide type epoxy resins such as YSLV 50TE (manufactured by Tohto Kasei Co., Ltd.); ether type epoxy resins such as YSLV 80DE (manufactured by Tohto Kasei Co., Ltd.); dicyclopentadiene type epoxy resins such as EP- 4088S and EP4088L (manufactured by ADEKA Corporation); naphthalene type epoxy resins such as SE-80, SE-90, manufactured by Shin A T&C; glycidyl amine type epoxy resins such as Epikote 630 (manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon 430 (manufactured by Dainippon Ink and Chemicals Inc.) and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company Inc.); alkylpolyol type epoxy resins such as ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiclon 726 (manufactured by Dainippon Ink and Chemicals Inc.), Epolight 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.) and Denacol EX-611 (manufactured by Nagase ChemteX Corporation); rubber modified type epoxy resins such as YR-450,YR-207 (all manufactured by Tohto Kasei Co., Ltd.) and Epolead PB (manufactured by Daicel Chemical Industries, Ltd.); glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX Corporation); bisphenol A type episulfide resins such as Epikote YL-7000
(manufactured by Japan Epoxy Resin Co., Ltd.); and others such as YDC- 1312, YSLV-BOXY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), Epikote 1031, Epikote 1032 (all manufactured by Japan Epoxy Resin Co., Ltd.), EXA-7120 (manufactured by Dainippon Ink and Chemicals Inc.), TEPIC (manufactured by Nissan Chemical Industries, Ltd.). Examples of the commercially available phenol novolak type epoxy compound include Epiclon N-740, N-770, N-775 (all manufactured by Dainippon Ink and Chemicals Inc.), Epikote 152, Epikote 154 (all manufactured by Japan Epoxy Resin Co., Ltd.), and the like. Examples of the commercially available cresol novolak type epoxy compound include Epiclon N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP and N-672- EXP (all manufactured by Dainippon Ink and Chemicals Inc.); an example of the commercially available biphenyl novolak type epoxy compound is NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); examples of the commercially available trisphenol novolak type epoxy compound include EP1032S50 and EP1032H60 (all manufactured by Japan Epoxy Resin Co., Ltd.); examples of the commercially available dicyclopentadiene novolak type epoxy compound include XD-1000-L (manufactured by Nippon Kayaku Co., Ltd.) and HP-7200 (manufactured by Dainippon Ink and Chemicals Inc.); examples of the commercially available bisphenol A type epoxy compound include Epikote 828, Epikote 834, Epikote 1001, Epikote 1004 (all
manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon 850, Epiclon 860 and Epiclon 4055 (all manufactured by Dainippon Ink and Chemicals Inc.); examples of the commercially available bisphenol F type epoxy compound include Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epiclon 830 (manufactured by Dainippon Ink and Chemicals Inc.); an example of the commercially available 2,2'-diallyl bisphenol A type epoxy compound is RE-810NM
(manufactured by Nippon Kayaku Co., Ltd.); an example of the commercially available hydrogenated bisphenol type epoxy compound is ST-5080 (manufactured by Tohto Kasei Co., Ltd.); examples of the commercially available polyoxypropylene bisphenol A type epoxy compound include EP-4000 and EP-4005 (all manufactured by ADEKA Corporation); and the like. HP4032 and Epiclon EXA-4700 (all manufactured by Dainippon Ink and Chemicals Inc.); phenol novolak type epoxy resins such as Epiclon N-770 (manufactured by Dainippon Ink and Chemicals Inc.); orthocresol novolak type epoxy resins such as Epiclon N-670-EXP-S
(manufactured by Dainippon Ink and Chemicals Inc.); dicyclopentadiene novolak type epoxy resins such as Epiclon HP7200 (manufactured by Dainippon Ink and Chemicals Inc.); biphenyl novolak type epoxy resins such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); naphthalene phenol novolak type epoxy resins such as ESN-165S (manufactured by Tohto Kasei Co.)
[0014] Examples of the alicyclic epoxy compounds useful in synthesizing the inventive resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring and cyclohexene oxide- or cyclopentene oxide containing compounds obtained by epoxidizing cyclohexene ring or cyclopentene ring-containing compounds. Specific examples include hydro genated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4- epoxycyclohexanecarboxylate, 3 ,4-epoxy-l-methyl cyclohexyl-3 ,4-epoxy- 1 - methylcyclohexanecarboxylate, 6-methyl-3 ,4-epoxycyclohexylmethyl-6-methyl-3 ,4-epoxy- cyclohexanecarboxylate, 3 ,4-epoxy-3 -methylcyclohexylmethyl 3 ,4-epoxy-3 - methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcylcohexylmethyl-3,4-epoxy-5- methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane- metadioxane, bis(3 ,4-epoxycyclohexylmethyl)adipate, 3 ,4-epoxy-6-methylcyclohexyl carboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide,
ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctylepoxyhexahydrophthalate, and di-2- ethylhexyl epoxyhexahydrophthalate .
[0015] Some of these alicyclic epoxy resins are commercially available under the following trade designations: UVR-6100, UVR-6105, UVR-6110, UVR-6128, and UVR-6200 (products of Union Carbide Corporation); CELLOXIDE 2021, CELLOXIDE 2021P,
CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 2000,
CELLOXIDE 3000, CYCLMER A200, CYCLMER MIOO, CYCLMER MlOl, EPOLEAD GT- 301, EPOLEAD GT-302, EPOLEAD 401, EPOLEAD 403, ETHB, and EPOLEADHD 300 (from Daicel Chemical Industries, Ltd.); KRM-21 10, and KRM-2199 (from ADEKA
Corporation). [0016] In addition to the curable polymers of the present invention, ODF sealant compositions may also include a free radical initiator (which may be triggered by exposure to elevated temperature conditions or radiation in the electromagnetic spectrum) and a curing agent. In embodiments where an epoxide ring is present, a latent epoxy curing agent may also be employed.
[0017] Useful thermal free radical initiators include organic peroxides and azo compounds, examples of which include: azo free radical initiators such as AIBN
(azodiisobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethyl valeronitrile), 2,2'-azobis(2,4- dimethyl valeronitrile), dimethyl 2,2'-azobis(2-ethylpropionate), 2,2'-azobis(2- methylbutyronitrile), 1,1,1 -azobis(cyclohexane- 1 -carbonitrile), 2,2'-azobis [N-(2-propenyl)-2- methylpropionamide]; dialkyl peroxide free radical initiators such as l,l-di-(butylperoxy-3,3,5- trimethyl cyclohexane); alkyl perester free radical initiators such as TBPEH (t-butyl per-2- ethylhexanoate); diacyl peroxide free radical initiators such as benzoyl peroxide; peroxy dicarbonate radical initiators such as ethyl hexyl percarbonate; ketone peroxide initiators such as methyl ethyl ketone peroxide, bis(t-butyl peroxide) diisopropylbenzene, t-butylperbenzoate, t- butyl peroxy neodecanoate, and combinations thereof.
[0018] Further examples of organic peroxide free radical initiators include dilauroyl peroxide, 2,2-di(4,4-di(tert-butylperoxy)cyclohexyl)propane, di(tert-butylperoxyisopropyl) benzene, di(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, 2,3-dimethyl-2,3-diphenylbutane, dicumyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, tert-butyl monoperoxymaleate, 2,5-dimethyl-2,5-di(tert- butylperoxy)hexane, tert-butylperoxy 2-ethylhexyl carbonate, tert-amyl peroxy-2- ethylhexanoate, tert-amyl peroxypivalate, tert-amylperoxy 2-ethylhexyl carbonate, 2,5-dimethyl- 2,5-di(2-ethylhexanoylperoxy) hexane 2,5-dimethyl-2,5-di(tert-butylperoxy) hexpe-3, di(3- methoxybutyl)peroxydicarbonate, diisobutyryl peroxide, tert-butyl peroxy-2-ethylhexanoate (TRIGONOX 21 S), 1,1 -di(tert-butylperoxy)cyclohexane, tert-butyl peroxyneodecanoate, tert- butyl peroxypivalate, tert-butyl peroxyneoheptanoate, tert-butyl peroxydiethylacetate, l,l-di(tert- butylperoxy)-3,3,5-trimethylcyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-l,4,7-triperoxonane, di(3,5,5-trimethylhexanoyl) peroxide, tert-butyl peroxy-3,5,5-trimethyl hexanoate, 1,1,3,3- tetramethylbutyl peroxy-2-ethylhexanoate, 1,1 ,3,3- tetrametbylbutyl peroxyneodecanoate, tert- butyl peroxy-3,5,5-trimethyl hexanoate, cumyl peroxyneodecanoate, di-tert-butyl peroxide, tert- butylperoxy isopropyl carbonate, tert-butyl peroxybenzoate, di(2-ethylhexyl) peroxydicarbonate, tert-butyl peroxyacetate, isopropylcumyl hydroperoxide, tert-butyl cumyl peroxide, and combinations thereof.
[0019] The thermal free radical initiators with a higher decomposition rate is ordinarily desired, as this can generate free radicals more easily at common cure temperatures (such as in the range of 80 to 130°C) and give faster cure speed, which can reduce the contact time between liquid resin and liquid crystal, and reduce the liquid crystal contamination. On the other hand, if the decomposition rate of initiator is too high, the viscosity stability at room temperature will be influenced and thereby reducing the work life of the sealant.
[0020] A convenient way of expressing the decomposition rate of an initiator at a specified temperature is in terms of its half-life i.e., the time required to decompose one-half of the peroxide originally present. To compare reactivity of different initiators, the temperature at which each initiator has a half-life ("T^") of 10 hours is used. The most reactive (fastest) initiator would be the one with the lowest 10 hour Ύ Α temperature.
[0021] In the present invention, the thermal free radical initiator with a 10 hour T] 2 temperature of 30 to 80°C is preferred, and with a 10 hour Ti/2 temperature of 40-70°C is more preferred.
[0022] To balance the reactivity and viscosity stability of the composition, the thermal free radical initiator used in the resin composition is in an amount of usually 0.01 to 3 parts by weight, and preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the inventive resin in the curable composition of the present invention.
[0023] Useful UV free radical initiators include Norrish type I cleavage photoinitiators that are commercially available from CIBA and BASF. These photoinitiators are used in the amount 0.1-5wt%, more preferably in about 0.2 to 3wt% in the formulation. [0024] Examples of useful epoxy curing agent include but are not limited to the Ajicure series of hardeners available from Ajinomoto Fine-Techno Co., Inc,; the Amicure series of curing agents available from Air products and the JERCURE™ products available from
Mitsubushi Chemical. These curing agents or hardeners or accelerators are used in the amount of about 1% to about 50 % by weight of the total composition, more preferably from about 5% to about 20% by weight of the total composition.
[0025] The curable composition may optionally contain, as desired, a further component capable of a photopolymerization reaction such as a vinyl ether compound. In addition, the curable composition may further comprise additives, resin components and the like to improve or modify properties such as flowability, dispensing or printing property, storage property, curing property and physical property after curing.
[0026] Various additives may be contained in the composition as desired, for example, organic or inorganic fillers, thixotropic agents, silane coupling agents, diluents, modifiers, coloring agents such as pigments and dyes, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents and the like; however it is not limited to these. In particular, the composition preferably comprises an additive selected from the group consisting of organic or inorganic filler, a thixotropic agent, and a silane coupling agent. These additives may be present in amounts of about 0.1% to about 50% by weight of the total composition, more preferably from about 2% to about 10% by weight of the total composition.
[0027] The filler may include inorganic fillers such as silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, barium sulphate, gypsum, calcium silicate, talc, glass bead, sericite activated white earth, bentonite, aluminum nitride, silicon nitride, and the like; meanwhile, organic fillers such as poly(methyl) methacrylate, poly(ethyl) methacrylate, poly(propyl) methacrylate, poly(butyl) methacrylate, butylacrylate-methacrylic acid-(methyl) methacrylate copolymer, polyacrylonitrile, polystyrene, polybutadiene,
polypentadiene, polyisoprene, polyisopropylene, and the like. These may be used alone or in combination. These fillers may be present in amounts of about 1% to about 80%, more preferably from about 5% to about 30% by weight of the total composition.
[0028] The thixotropic agent may include, but is not limited to, talc, fume silica, superfine surface-treated calcium carbonate, fine particle alumina, plate-like alumina; layered compounds such as montmorillonite, spicular compounds such as aluminum borate whisker, and the like. Among them, talc, fume silica and fine alumina are particularly desired. These agents may be present in amounts of about 1% to about 50%, more preferably from about 1% to about 30% by weight of the total composition.
[0029] The silane coupling agent may include, but is not limited to, γ- aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxylsilane, and the like.
[0030] The curable composition according to the present invention may be obtained by mixing the aforementioned each component by means of, for example, a mixer such as a stirrer having stirring blades and a three roll mill. The composition is liquid at ambient with the viscosity of 200-400 Pa.s (at 25°C) at 1.5s-l shear rate.
[0031] The present invention also relates to a method for manufacturing a liquid crystal display having a liquid crystal layer between a first substrate and a second substrate, by means of a liquid crystal one-drop-filling process. The method comprises the steps of:
(a) applying the curable composition described in the present invention on a sealing region at periphery of a surface of the first substrate;
(b) dropping liquid crystal on a central area encircled by the sealing region of the surface of the first substrate;
(c) overlaying the second substrate on the first substrate;
(d) performing partial curing by UV-irradiating the curable composition, and
(e) performing final curing by heating the curable composition. [0032] The first substrate and the second substrate used in the present invention are usually transparent glass substrates. Generally, transparent electrodes, active matrix elements (such as TFT), alignment film(s), a color filter and the like are formed on at least one of the opposed faces of the two substrates. These constitutions may be modified according to the type of the LCD. The manufacturing method according to the present invention may be thought to be applied for any type of the LCD.
[0033] In the step (a), the curable composition is applied on the periphery portion of the surface of the first substrate so as to lap around the substrate circumference in a frame shape. The portion where the curable composition is applied in a frame shape is referred as a seal region. The curable composition can be applied by a known method such as screen printing and dispensing.
[0034] In the step (b), the liquid crystal is then dropped onto the center region surrounded by the seal region in the frame shape on the surface of the first substrate. This step is preferably conducted under reduced pressure.
[0035] In the step (c), said second substrate is then placed over said first substrate, and
UV-irradiated in the step (d). By the UV-irradiation, the curable composition cures partially and shows the strength at a level that displacement does not occur by handling, whereby the two substrates are temporally fixed. Generally, the radiation time is preferably short, for example not longer than 5 minutes, preferably not longer than 3 minutes, more preferably not longer than 1 minute.
[0036] In the step (e), heating the curable composition allows it to achieve the final curing strength, whereby the two substrates are finally bonded. The thermal curing in the step (e) is generally heated at a temperature of 80 to 130°C, and preferably of 100 to 120°C, with the heating time of 30 minutes to 3 hours, typically 1 hour.
[0037] By the aforementioned process, the major part of the LCD panel is completed. EXAMPLES
Example 1:
Example 1
Figure imgf000016_0001
[0038] To a 250mL of 3 necked flask equipped with a mechanical stirrer were added
Epiclon 850CRP (23.49g, 69mmol), 4-vinylbenzyl thioacetate (17.25g, 89mmol), potassium phenoxide (0.4g, 3mmol) and 18-Crown-6 (0.8g, 3mmol) and the mixture stirred at 60°C for 3h. Infrared (IR) spectroscopy indicated the appearance of a new carbonyl band at 1730cm"1 for the acetate and disappearance of the thioacetate band at 1688cm"1. After cooling the mixture, potassium carbonate (12.4g, 89 mmol) in 150 ml of methanol were added and the mixture stirred at room temperature for 30 minutes. The mixture was filtered and then washed with ethyl acetate. The organic layer was collected, washed four times with deionized water and dried over anhydrous Na2S04. After filtration, the organic layer was stirred with 5g of silica gel and 4g of sillitin for lh, and then filtered and washed with 50mL of ethyl acetate. 2000ppm of t- butylcatechol was added and the solvent evaporated to yield the BPA styrenyl-epoxy resin as an oil (40g, 89%) Example 2:
Example 2
Figure imgf000017_0001
[0039] To a 250mL of 3 necked flask equipped with a mechanical stirrer were added
Epiclon 850CRP (26.17g, 76mmol), 4-acetoxystyrene (16.2g, 99mmol), tetrabutylammonium bromide (1.24g, 3mmol) and the mixture was stirred at 90°C for 6h. IR Spectroscopy indicated the appearance of a new carbonyl band at 1743cm"1 for the alkyl acetate and disappearance of the phenylacetate band at 1759cm"1. After cooling, potassium carbonate (12.4g, 89 mmol) in 150 ml of methanol were added and the mixture stirred at room temperature for lh. The solid was filtered and washed with ethyl acetate. The organic layer was washed several times with deionized water and dried over anhydrous Na2S04. After filtration, 5g of silica gel and 4g of sillitin were added and stirred for lh. The solids were filtered and washed with 50mL of ethyl acetate. 2000ppm of t-butylcatechol was added and the solvent evaporated to yield the BPA styrenyl epoxy resin as a viscous liquid (32g, 76%).
Example 3:
Example 3
Figure imgf000018_0001
[0040] To a 250mL of 3 necked flask equipped with a magnetic stirrer was added sodium hydride (3.58g of 60% dispersion in oil, 89mmol) under a nitrogen atmosphere. Heptane (50mL) was added to the flask and stirring continued for 15 minutes, after which time the heptane was removed and lOOmL of THF was added in its stead. The mixture was cooled with ice-water. 4- Vinylbenzyl alcohol (lOg, 74mmol) in THF (lOmL) was added and stirring continued for lh at the same temperature. Epiclon 850CRP (25.34g, 74mmol) in THF (25mL) was added tothe mixture and stirring continued for 5h at room temperature. Any excess NaH was quenched by the slow addition of water. The mixture was extracted with ethyl acetate (300mL), and the organic layer was washed 4 times with deionized water and dried over anhydrous Na2S04. After filtration, 5g of silica gel and 4g of sillitin were added and the washed and dried mixture stin-ed for lh. The mixture was filtered and washed with 50mL of ethyl acetate. 2000ppm of t- butylcatechol was added and the solvent evaporated to yield the styrenyl epoxy resin as a viscous liquid. Example 4:
Example 4
Figure imgf000019_0001
[0041] To a 3 necked 50mL flask equipped with an inlet tube for nitrogen gas, a thermometer, a condenser and a dropping funnel were added with stirring allylsuccinic anhydride (13.95g, 99mmol) and latinum-l,3-divinyl-l,l,3,3-tetramethyldisiloxane complex (13mg), and the mixture was heated to 100°C. 1,1,3,3,5,5-Hexamethyltrisiloxane (10.38g, 49mmol) was added drop- ise to the reaction mixture over a time period of one hour. The temperature of the reaction was controlled to remain within the temperature range of 90-110°C for 30 minutes. The intermediate hydrosilylated difunctional anhydride was so produced.
[0042] 4-Aminostrene (5.07g, 42mmol) in toluene (20mL) was added to a lOOmL 3 necked flask equipped with a temperature control, condenser and magnetic stir bar. The intermediate anhydride from above (10.4g, 21mmol) was added portionwise to the flask and the resulting mixture was stirred at room temperature for 30 minutes. Acetic anhydride (8.7g, 85mmol) and pyridine (6.9mL, 85mmol) were added to the mixture, and stirring continued at 60°C for 2 hour. IR Spectroscopy indicated the appearance of a new carbonyl band at 1710 cm"1. After cooling the mixture to room temperature 250mL of ethyl acetate was added and the organic layer washed twice with water, twice with 5% aqueous HC1, water, 5% NaOH solution and water. After drying over anhydrous Na2S04, 500ppm of BHT was added to the organic layer and the solvent was evaporated to yield the product as a solid (12g, 81%). Example 5:
Example 5
Figure imgf000020_0001
[0043] To a 500mL 3 necked flask equipped with a condenser, nitrogen inlet and magnetic stir bar was added a 60% sodium hydride dispersion in oil (lOg, 248mmol) followed by 60mL of heptane. The mixture was stirred for 10 minutes under nitrogen, and the sodium hydride slurry was allowed to settle so the heptane could be removed from the flask. In its stead, 120mL of DMF was added to the flask and the slurry was cooled with ice-water mixture. 2- Imidazolidone (9.8g, 113mmol) was added portionwise with stirring over a period of 15 minutes. After stirring for lh at the same temperature, 4-vinylbenzyl chloride (34.7g, 227mmol) was added dropwise over 15 minutes and the reaction mixture was allowed to continue to stir for 24h at room temperature. The reaction mixture was cooled with ice, quenched with water s, extracted with 500mL of ethyl acetate, washed 4 times with water and dried over anhydrous Na2S04. lOOOppm of t-butylcatechol was added and the solvent evaporated under vacuum.
N,N'-(4-Vinylbenzyl)ethylene urea was afforded as a solid (31g, 86%)
Example 6:
Example 6
Figure imgf000021_0001
[0044] A mixture of isophthaleic acid (15g, 90mmol) and potassium carbonate (24.96g,
180mmol) in DMF (150mL) was stirred at 60°C for lh in the presence of 1500ppm of t- butylcatechol. A solution of 4-vinylbenzyl chloride (24.96g, 180mmol) in DMF (50mL) was added. A slight exotherm was seen (temperature increased by about 10-15°C). In about 30 minutes, the color of 4-vinylbenzyl chloride (dark yellow) disappears and a white turbid solution forms. The reaction was stirred at 60°C for 24h. After cooling to RT the solid was filtered off and washed with 400mL of ethyl acetate. The organic layer was washed 4 times with water to remove all of the DMF and dried over anhydrous Na2S04. After filtering, the solvent was evaporated in rotovap under vacuum to give corresponding 4-vinylbenzyl ester as a low melting light yellow solid (27.8g, 77%).
Example 7:
Figure imgf000022_0001
[0045] To a 1L 4 necked flask equipped with a mechanical stirrer were added EP 4088S epoxy resin (36.7g, 118mmol), 4-vinylbenzoic acid (37g, 249mmol), Hycat 2000S (720mg, 1 wt %) and t-butyl catechol (360mg, 5000ppm) in toluene (78mL). The mixture was stirred at 65°C for about 36 hours. After cooling to room temperature, 500mL of ethyl acetate was added and the organic layer washed twice with aqueous NaHC03 solution (2 x 150mL), twice with 0.1N NaOH solution and several times with deionized water. About 3000ppm of t-butyl catechol was added to the organic layer, which was then dried over anhydrous Na2S04. After filtering away the drying agent, the organic layer was further stirred with sillitin (lOg) and silica gel (lOg) for lh, and then filtered away. The solvent was evaporated to yield the hydroxy ester as a viscous oil.

Claims

What is Claimed is:
1. A resin comprising the structure:
I
Figure imgf000023_0001
wherein Q may be selected from:
Figure imgf000023_0002
wherein R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene or
heterocycloarylenes; the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene and
heterocycloarylenes can optionally contain O or S or hydroxyl group;
Ri is H or methyl;
X is selected from CH2,
Figure imgf000024_0001
ni and n3 are each independently 0-10;
n2 is 1-10;
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene;
Z is a covalent bond linking the aryl group to the oxygen, a carbonyl group, or hydrocarbylene linker group; and
R2 is a substituent on the aromatic ring selected from the group consisting of alkyl, alkoxy, aryloxy, halide, aliphatic and aromatic groups.
2. A resin comprising the structure:
II
Figure imgf000024_0002
wherein Q may be selected from:
Figure imgf000024_0003
R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene or
heterocycloarylenes; the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene and
heterocycloarylenes can optionally contain O or S or hydroxyl group;
Ri is H or methyl;
X is selected from CH
Figure imgf000025_0001
m and n3 are each independently 0-10;
n2 is 1-10;
Y is arylene, alkylene, alkenylene, aralkylene, cycloalkylene, bicycloalkylene or tricycloalkylene;
Z is a covalent bond linking the aryl group to the sulfur, or a hydrocarbylene group; and R2 is a substituent on the aromatic ring selected from the group consisting of alkyl, alkoxy, aryloxy, halide, aliphatic and aromatic groups.
3. A resin comprising the structure:
III
Figure imgf000025_0002
wherein Yi and Y2 can be same or different and are polymerizable functionalities selected from vinylbenzyl, vinylaryl, (meth)acrylate, allyl, cinnamyl and glycidyl; Xi and X2 area covalent bonds connecting the Yi and Y2 groups to the nitrogen, or may be selected from one or more of alkylene or cycloalkylene each of which may optionally contain one or more hetero atoms such as oxygen, sulfur or nitrogen;
Ri is a substituent on the cyclic urea ring selected from alkyl, cycloalkyl, aryl, aralkyl; and
n = l-10. resin comprising the structure:
Figure imgf000026_0001
wherein X is a hetero atom selected from O, S, or N; or a functionality selected from ester, urethane, urea, imide, carbonate; or a group selected from alkylene, cycloalkyene, oxyalkylene optionally containing hydroxyl functionality at any position or one or more atoms selected from O, S, or N at any position;
R is a multivalent hydrocarbyl linker selected from linear or branched alkyls, linear or branched cycloalkyls, alkylenes, cycloalkylenes, bicycloalkylenes, tricycloalkylenes, linear or branched alkylenes, linear or branched cycloalkylenes, linear or branched alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene or
heterocycloarylenes; the alkyls, cycloalkyls, alkylenes, cycloalkylenes, alkenylenes, arylenes, aralkylenes, arylbicycloalkylenes, aryltricycloalkylenes, bicycloalkylarylenes,
tricycloalkylarylenes, bisphenylenes, cycloalkylarylenes, heterocycloalkylene and
heterocycloarylenes can optionally contain O or S or hydroxyl group; or R may also be silicone or siloxane in combination with one or more of the above-mentioned multivalent linkers.
5. An ODF sealant composition comprising the resin of claim 1 and a material selected from the group consisting of photoinitiators, free radical initiators, curing agents, fillers and combinations thereof.
6. The ODF sealant composition of claim 5 further comprising a material selected from the group consisting of photopolymerizable compounds, thermoset resins, thixotropic agents, silane coupling agents, diluents, modifiers, coloring agents, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents and combinations thereof.
7. An ODF sealant composition comprising the resin of claim 2 and a material selected from the group consisting of photoinitiators, free radical initiators, curing agents, fillers and combinations thereof.
8. The ODF sealant composition of claim 7 further comprising including and a material selected from the group consisting of photopolymerizable compounds, thermoset resins, thixotropic agents, silane coupling agents, diluents, modifiers, coloring agents, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents and combinations thereof.
9. An ODF sealant composition comprising the resin of claim 3 and a material selected from the group consisting of photoinitiators, free radical initiators, curing agents, fillers and combinations thereof.
10. The ODF sealant composition of claim 9 further comprising a material selected from the group consisting of photopolymerizable compounds, thermoset resins, thixotropic agents, silane coupling agents, diluents, modifiers, coloring agents, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents and combinations thereof.
11. An ODF sealant composition comprising the resin of claim 4 and a material selected from the group consisting of photoinitiators, free radical initiators, curing agents, fillers and combinations thereof.
12. The ODF sealant composition of claim 11 further comprising a material selected from the group consisting of photopolymerizable compounds, thermoset resins, thixotropic agents, silane coupling agents, diluents, modifiers, coloring agents, surfactants, preservatives, stabilizers, plasticizers, lubricants, defoamers, leveling agents and combinations thereof.
13. A compound selected from
Figure imgf000028_0001
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000029_0002
Figure imgf000029_0003
28
Figure imgf000030_0001
29
PCT/US2018/033371 2017-05-18 2018-05-18 Curable compositions for one drop sealant applications WO2018213695A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3624180A (en) * 1968-08-07 1971-11-30 Rolf Schmid Heat-curable compositions of matter
WO2016095437A1 (en) * 2014-12-19 2016-06-23 广东生益科技股份有限公司 Thermosetting resin composition and application thereof
WO2017008242A1 (en) * 2015-07-14 2017-01-19 Henkel IP & Holding GmbH Monomeric and oligomeric resins for one drop fill sealant application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3624180A (en) * 1968-08-07 1971-11-30 Rolf Schmid Heat-curable compositions of matter
WO2016095437A1 (en) * 2014-12-19 2016-06-23 广东生益科技股份有限公司 Thermosetting resin composition and application thereof
WO2017008242A1 (en) * 2015-07-14 2017-01-19 Henkel IP & Holding GmbH Monomeric and oligomeric resins for one drop fill sealant application

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