WO2014057871A1 - グリシジルエーテル系化合物、液晶シール剤及びグリシジルエーテル系化合物の製造方法 - Google Patents

グリシジルエーテル系化合物、液晶シール剤及びグリシジルエーテル系化合物の製造方法 Download PDF

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WO2014057871A1
WO2014057871A1 PCT/JP2013/077036 JP2013077036W WO2014057871A1 WO 2014057871 A1 WO2014057871 A1 WO 2014057871A1 JP 2013077036 W JP2013077036 W JP 2013077036W WO 2014057871 A1 WO2014057871 A1 WO 2014057871A1
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group
compound
liquid crystal
meth
glycidyl
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PCT/JP2013/077036
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English (en)
French (fr)
Japanese (ja)
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大晃 臼井
良爾 堀越
健介 宮崎
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協立化学産業株式会社
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Priority to CN201380052675.4A priority Critical patent/CN104718231B/zh
Priority to KR1020157011942A priority patent/KR102056074B1/ko
Priority to JP2014540827A priority patent/JP6310852B2/ja
Publication of WO2014057871A1 publication Critical patent/WO2014057871A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • 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
    • C07D303/31—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals in which the oxirane rings are condensed with a carbocyclic ring system having three or more relevant rings
    • 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
    • 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 a glycidyl ether compound, a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.
  • liquid crystal display device such as a liquid crystal panel
  • a liquid crystal sealant is applied to the outer periphery of one of the two substrates constituting the liquid crystal panel, and a predetermined amount of liquid crystal is dropped on either substrate.
  • a liquid crystal dropping method is widely used in which two substrates are bonded together under vacuum and then returned to atmospheric pressure to fill the liquid crystal and cure the liquid crystal sealant.
  • a radical polymerization reactive compound mainly composed of an epoxy acrylate compound is widely used as a liquid crystal sealant from the viewpoint of high-speed curing (see, for example, JP-A-2007-297470).
  • a seal is applied to the base in the form of a frame to form a frame seal, the liquid crystal is dropped inside the frame, vacuum is applied to the panel, and UV irradiation is performed to lightly cure the liquid crystal sealant.
  • heat curing is performed at a temperature equal to or higher than the NI point (Nematic (Isotropic point) of the liquid crystal to thermally cure the liquid crystal sealant and simultaneously align the liquid crystal.
  • the conventional radical polymerization reactive liquid crystal sealant mainly composed of an epoxy compound containing an epoxy / acrylic compound has not been able to sufficiently meet such a demand.
  • the problem of the present invention is that the liquid crystal sealing agent can be strongly bonded and cured even when the liquid crystal sealing agent is applied with a narrow seal width and the substrate is bonded in the liquid crystal dropping method, which affects the liquid crystal orientation. It is an object of the present invention to provide a glycidyl ether compound that is difficult to give, a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.
  • n 1 is a number in the range of 2-30, m is a number in the range of 1-5, X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms, Y is each independently an alkylene group having 2 to 4 carbon atoms, R is independently of each other a hydrogen atom, a glycidyl group, a methylglycidyl group, a group 1: —CH 2 —CH (OR 1 ) —CH 2 —O—R 2 or a group 2: —CH 2 —C (CH 3 ) (OR 1 ) —CH 2 —O—R 2 (wherein R 1 is a hydrogen atom or a (meth) acryloyl group, and R 2 is a (meth) acryloyl group),
  • R ′ independently of one another, is a hydrogen atom or a methyl group; In R, the total number
  • n 2 is a number in the range of 2-30, Y is each independently an alkylene group having 2 to 4 carbon atoms, R 11 is each independently a hydrogen atom, a glycidyl group or a methyl glycidyl group)
  • R 12 is independently of each other a hydrogen atom, a glycidyl group, a methyl glycidyl group, a group 1: —CH 2 —CH (OR 21 ) —CH 2 —O—R 22 or a group 2: —CH 2 —C (CH 3 ) a compound represented by (OR 21 ) —CH 2 —O—R 22 (wherein R 21 is a hydrogen atom or a (meth) acryloyl group, and R 22 is a (meth) acryloyl group).
  • It is a manufacturing method of the glycidyl ether type compound represented by Formula (1) of said [1] description including the process with which D is made to react.
  • the liquid crystal sealant in the liquid crystal dropping method, even when the liquid crystal sealant is applied with a narrow seal width and the substrate is bonded, the liquid crystal sealant can be strongly bonded and cured, which affects the liquid crystal orientation. It is possible to provide a glycidyl ether compound that is difficult to give, a liquid crystal sealant containing the glycidyl ether compound, and a method for producing the glycidyl ether compound.
  • the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. .
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
  • (meth) acryloyl means methacryloyl and / or acryloyl
  • (meth) acrylate means methacrylate and / or acrylate.
  • Compound A The glycidyl ether compound of the present invention (hereinafter also referred to as compound A) is represented by the following formula (1).
  • n 1 is a number in the range of 2 to 30, and m is a number in the range of 1 to 5.
  • X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms.
  • Y is each independently an alkylene group having 2 to 4 carbon atoms.
  • R is independently of each other a hydrogen atom, a glycidyl group, a methylglycidyl group, a group 1: —CH 2 —CH (OR 1 ) —CH 2 —O—R 2 or a group 2: —CH 2 —C (CH 3 ) (OR 1 ) —CH 2 —O—R 2 (wherein R 1 is a hydrogen atom or a (meth) acryloyl group, and R 2 is a (meth) acryloyl group).
  • R ′ is, independently of each other, a hydrogen atom or a methyl group.
  • R when the total number x of the total of the glycidyl group, the methyl glycidyl group, the group 1 and the group 2 is 2 or more, and the R includes the group 1 or the group 2, the glycidyl group And the ratio (y / z) of the average number y of the total of the methyl glycidyl groups and the total number z of the total of the groups 1 and 2 is 10/90 to 90/10.
  • N 1 is a number in the range of 3 to 25, preferably a number in the range of 5 to 20, more preferably a number in the range of 5 to 15, more preferably in the range of 7 to 10. Is a number. N 1 is derived from the number of repeating units of the compound represented by formula (2) (compound C), that is, n 2 .
  • m Is a number in the range of 1 to 5, preferably a number in the range of 1 to 4, more preferably a number in the range of 1 to 3, and still more preferably a number in the range of 1 to 2.
  • m can be estimated from the reaction equivalent ratio (preparation amount) of the compound C and the compound D which are raw materials of the compound A.
  • n 1 and m can also be measured by GPC.
  • Y is each independently an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, or the like. Y is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • the average number x of the total of glycidyl group, methylglycidyl group, group 1 and group 2 is influenced by workability of the liquid crystal sealant such as coating property affected by viscosity, for example, crosslink density. From the viewpoint of physical properties such as strength after curing, it is 2 or more, preferably 2 to 2 m + 2, more preferably 2 m to 2 m + 2, and further preferably 2 m + 1 to 2 m + 2.
  • X represents the average molecular weight and molecular weight distribution of Compound A by high performance liquid chromatography (HPLC) and liquid chromatography mass spectrometry (LC-MS), and by measuring n 1 and m by GPC, Can be calculated.
  • HPLC high performance liquid chromatography
  • LC-MS liquid chromatography mass spectrometry
  • the ratio of the average number y of the total of the glycidyl group and the methyl glycidyl group and the average number z of the total of the group 1 and the group 2 (Y / z) is 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, still more preferably 40/60 to 60/40. .
  • each R is independently a hydrogen atom, glycidyl group, methyl glycidyl group, group 1 or group 2, and preferably a hydrogen atom, glycidyl group or group 1.
  • R ' is preferably a hydrogen atom.
  • the viscosity of compound A is preferably 1000 to 1000000 mPa ⁇ s, more preferably 3000 to 700000 mPa ⁇ s, and still more preferably, from the viewpoint of securing an appropriate viscosity for the liquid crystal sealant. It is 5000 to 500000 mPa ⁇ s, more preferably 7000 to 250,000 mPa ⁇ s, and further preferably 9000 to 200000 mPa ⁇ s. The viscosity is measured at 25 ° C. using an E-type viscometer.
  • the viscosity of compound A can be adjusted, for example, by changing n 1 and m in compound A and / or changing the abundance ratio of hydroxyl groups in compound A.
  • the epoxy equivalent is preferably 100 to 3000 g / eq, more preferably 150 to 2000 g / eq from the viewpoint of strong adhesiveness.
  • the epoxy equivalent of compound A can be adjusted by the average molecular weight of compound A and the number of epoxy groups per repeating unit. For example, it can be adjusted by the ratio of epoxidizing the hydroxyl group of compound P and by the ratio of (meth) acrylate modification of the epoxy group of reactant Q.
  • Compound A is a liquid crystal dropping method, and even when it comes into contact with the liquid crystal in an uncured state, it hardly affects the alignment of the liquid crystal (change in the NI point is small) and does not easily disturb the alignment of the liquid crystal. Preferred as an agent.
  • Liquid crystal sealant containing compound A A liquid crystal sealant containing compound A (hereinafter also referred to as “composition”) is excellent in strong adhesion.
  • the content of compound A is preferably 10 to 10 in the reactive curable component of the liquid crystal sealant (for example, a component that can be cured by reaction with light and / or heating).
  • 100% by weight more preferably 20 to 100% by weight, still more preferably 30 to 100% by weight, still more preferably 40 to 100% by weight, still more preferably 50 to 100% by weight, More preferred is 60 to 100% by weight, still more preferred is 70 to 100% by weight, still more preferred is 80 to 100% by weight, still more preferred is 90 to 100% by weight, still more preferred is 100% by weight. It is.
  • the liquid crystal sealant containing the compound significantly improves the strong adhesiveness. That is, the liquid crystal sealant preferably contains, in addition to compound A, compound B having an ethylenically unsaturated group and / or an epoxy group other than compound A.
  • Examples of the compound B having an ethylenically unsaturated group include (meth) acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, acrylamide compounds containing aromatics, and N-substituted acrylamide compounds.
  • Examples of (meth) acrylate compounds include fats represented by paracumylphenoxyethylene glycol (meth) acrylate, t-butyl (meth) acrylate, ethoxylated phenyl (meth) acrylate, benzyl (meth) acrylate, and glycidyl (meth) acrylate.
  • Examples of the ethylenically unsaturated group-containing compound include monofunctional, difunctional, trifunctional or polyfunctional radically polymerizable unsaturated compounds.
  • Monofunctional radically polymerizable unsaturated compounds include hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and isooctyl from the viewpoint of ensuring composition viscosity, film hardness, and flexibility.
  • One or more compounds selected from the group consisting of acrylate, lauryl (meth) acrylate, tert-butyl (meth) acrylate and diethylene glycol monoethyl ether (meth) acrylate are preferred, Runiru (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, one or more compounds selected from the group consisting of dicyclopentanyl (meth) acrylate and cyclohexyl (meth) acrylate are more preferred.
  • tricyclodecane dimethanol di (meth) acrylate dimethylol dicyclopentanedi (meth) acrylate, EO-modified 1,6-hexanediol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, silicone
  • dimethylol dicyclopentane di (meth) acrylate and / or modified bisphenol A di (meth) acrylate is preferably used.
  • (meth) acrylates having no hydroxyl group and having a bisphenol A skeleton are preferable.
  • light acrylate BP-4EAL (EO addition product of bisphenol A), BP-4PA (PO addition of bisphenol A) Product diacrylate) and the like are commercially available.
  • Trifunctional or higher radical polymerizable unsaturated compounds include ECH-modified glycerol tri (meth) acrylate (trifunctional) and EO-modified glycerol tri (meth) acrylate from the viewpoint of ensuring composition viscosity, film hardness, and flexibility.
  • Trifunctional PO-modified glycerol tri (meth) acrylate (trifunctional), pentaerythritol tri (meth) acrylate (trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra (meth) acrylate
  • One or more compounds selected from the group consisting of (tetrafunctional) are preferable, and EO-modified glycerol tri (meth) acrylate and / or dipentaerythritol hexa (meth) acrylate are more preferable.
  • the compound B having an epoxy group is preferably a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol AD type epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a naphthalene type epoxy compound, or a hydrogen thereof. It is at least one compound selected from the group consisting of an additive compound and an alicyclic epoxy compound, more preferably at least one selected from the group consisting of a bisphenol A type epoxy compound, a bisphenol F type epoxy compound and a naphthalene type epoxy compound. It is a seed compound, and more preferably a bisphenol A type epoxy compound.
  • Specific examples of the bisphenol A type epoxy compound include EPICLON 850S, 860, 1055, and EPICLON 850CRP manufactured by DIC.
  • Specific examples of the hydrogenated bisphenol A type epoxy compound include KRM-2408 manufactured by ADEKA and YX-8034 manufactured by JER.
  • Specific examples of the bisphenol F-type epoxy compound include EPICLON 830S manufactured by DIC.
  • Specific examples of naphthalene type epoxy compounds include EPICLON HP-4032D and HP-7200H manufactured by DIC.
  • Specific examples of the phenol novolac type epoxy compound include EPICLON N-740 and N-770 manufactured by DIC.
  • Specific examples of the cresol novolac type epoxy compound include EPICLON N-660 and N-670 manufactured by DIC.
  • alicyclic epoxy compound examples include 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate (Celoxide 2021P manufactured by Daicel), 1,2: 8,9-diepoxy limonene.
  • Celoxide 3000 manufactured by Daicel 1,2-epoxy-4-vinylcyclohexane
  • MeHPE3150 1,2-epoxy-4- (2 of 2,2-bis (hydroxymethyl) -1-butanol -Oxiranyl) cyclohexane adduct
  • a partial (meth) acrylate-modified epoxy compound obtained by reacting an epoxy group-containing compound with a (meth) acrylic acid compound can also be used.
  • a partial (meth) acrylated epoxy compound obtained by reacting an epoxy compound with (meth) acrylic acid is more preferred.
  • a partial (meth) acrylated epoxy resin obtained by reacting a bisphenol A type epoxy resin and (meth) acrylic acid is obtained, for example, as follows. First, bisphenol A type epoxy resin and (meth) acrylic acid are added in the presence of a basic catalyst, preferably in the presence of a trivalent organic phosphoric acid compound and / or an amine compound. ⁇ 90 equivalent% is reacted. Next, the reaction product is purified by removing the basic catalyst by filtration, centrifugation, and / or washing with water.
  • a known basic catalyst used by a reaction between an epoxy resin and (meth) acrylic acid can be used.
  • a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.
  • the compound B preferably contains a radical curable compound containing an ethylenically unsaturated group-containing compound as a preferred example.
  • the liquid crystal sealant of the present invention contains a photopolymerization initiator (a compound that is activated by absorbing light energy and generates radicals) as a radical generation source when photopolymerizing compound A and / or compound B. be able to.
  • a polymerization initiator is not specifically limited, A well-known compound can be used as a polymerization initiator.
  • benzoins As polymerization initiators, benzoins, acetophenones, benzophenones, thioxanthones, ⁇ -acyloxime esters, phenylglyoxylates, benzyls, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoin ethers And anthraquinone polymerization initiators are preferable, and those having a reactive group that has low solubility in liquid crystals and does not gasify the decomposition product itself upon irradiation with light are preferable.
  • a preferable polymerization initiator of the present invention for example, the following:
  • EY Resin KR-2 manufactured by KS Corporation.
  • an amine curing agent such as an organic acid dihydrazide compound, imidazole and its derivatives, dicyandiamide, aromatic amine, epoxy-modified polyamine, polyaminourea and the like are preferable from the viewpoint of strong adhesiveness, and organic acid dihydrazide.
  • VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide) and LDH (octadecane- 1,18-dicarboxylic acid dihydrazide) is preferred.
  • VDH 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin
  • ADH adipic acid dihydrazide
  • UDH 7,11-octadecadiene-1,18-dicarbohydra
  • photosensitizer examples include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo and diazo compounds, halogen compounds, and photoreducible dyes from the viewpoint of curability.
  • photosensitizers include benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone; benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate.
  • Benzophenone derivatives such as 4,4′-bis (diethylamino) benzophenone; thioxanthone derivatives such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone; 2-chloroanthraquinone, 2-methylanthraquinone, etc.
  • Anthraquinone derivatives; acridone derivatives such as N-methylacridone and N-butylacridone; other ⁇ , ⁇ -diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compounds Etc.
  • These photosensitizers may be used alone or in combination of two or more.
  • a preferred photosensitizer is 2,4-diethylthioxanthone (for example, DETX-S manufactured by Nippon Kayaku).
  • the liquid crystal sealant of the present invention can contain a curing accelerator from the viewpoint of accelerating the curing reaction of the curable compound, and is preferably an imidazo such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole.
  • a curing accelerator from the viewpoint of accelerating the curing reaction of the curable compound, and is preferably an imidazo such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole.
  • a filler can be added from the viewpoints of viscosity control, further improvement in strength after curing, adhesion reliability, and suppression of linear expansion.
  • an inorganic filler and an organic filler can be used.
  • inorganic fillers calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride Is mentioned.
  • the organic filler include polymethyl methacrylate, polystyrene, a copolymer obtained by copolymerizing a monomer constituting these and another monomer, polyester fine particles, polyurethane fine particles, and rubber fine particles.
  • the average particle size of the particles constituting the filler is 0.1 to 3 ⁇ m, and more preferably 0.5 to 3 ⁇ m.
  • the average particle size of the filler is measured by a laser diffraction / scattering particle size distribution measuring device manufactured by HORIBA (for example, Partica LA-950V2 manufactured by HORIBA).
  • the liquid crystal sealant of the present invention can contain a silane coupling agent within the scope of the effects of the present invention.
  • the silane coupling agent is preferably tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethoxydiethoxy.
  • Tetraalkoxysilanes such as silane, dimethoxydiisopropoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltriethoxysilane, ethyltri Butoxysilane, cyclohexyltriethoxysilane, phenyltriisopropoxysilane, vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyl Trialkoxysilanes such as limethoxysilane; and at least one selected from the group consisting of dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, and phenylethy
  • the process for producing compound A of the present invention comprises: Following formula (2):
  • n 2 is a number in the range of 2 to 30, Y is independently an alkylene group having 2 to 4 carbon atoms, and R 11 is independently of each other a hydrogen atom, glycidyl Group C or a methyl glycidyl group),
  • X is an oxygen atom (O), an alkylene group having 1 to 4 carbon atoms or an alkylidene group having 2 to 4 carbon atoms
  • R 12 s independently of one another are a hydrogen atom, a glycidyl group, Methyl glycidyl group, group 1: —CH 2 —CH (OR 21 ) —CH 2 —O—R 22 or group 2: —CH 2 —C (CH 3 ) (OR 21 ) —CH 2 —O—R 22 ( Wherein R 21 is a hydrogen atom or a (meth) acryloyl group, and R 22 is a (meth) acryloyl group)].
  • N 2 in Compound C may be selected so that n 1 of Compound A falls within the above-mentioned range from the viewpoint of strong adhesiveness of Compound A, and is a number in the range of 3 to 25, preferably 5 to 20 The number is in the range, more preferably in the range of 5 to 15, and still more preferably in the range of 7 to 10.
  • the molecular weight (weight average molecular weight) of the compound C in which R 11 is a hydrogen atom is preferably 2000 or less.
  • Y in the compound C is an alkylene group having 2 to 4 carbon atoms, specifically, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, or the like.
  • Y is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
  • Compounds C and D are commercially available or can be easily prepared from commercially available compounds according to known methods.
  • compound C in which R 11 is a hydrogen atom and Y is an ethylene group those having various numbers of repeating units (n 2 ) as polyethylene glycol are available, and compounds having a desired range of n 2 May be appropriately selected.
  • N 2 can also be calculated in the same manner as n 1 .
  • the molecular weight of polyethylene glycol is preferably 2000 or less.
  • compound C in which R 11 is a hydrogen atom and Y is a propylene group compounds having various numbers of repeating units are available as polypropylene ether glycol.
  • polypropylene ether glycol examples include EXCENOL420, EXCENOL720, EXCENOL1020, EXCENOL2020 (above, manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned.
  • the molecular weight of polypropylene ether glycol is preferably 2000 or less.
  • compound C in which R 11 is a hydrogen atom and Y is a trimethylene group can be obtained, for example, as polytrimethylene ether glycol having various numbers of repeating units according to the method described in JP2013-515144A. It can be manufactured.
  • the molecular weight of polytrimethylene ether glycol is preferably 2000 or less.
  • compound C in which R 11 is a hydrogen atom and Y is a tetramethylene group those having various numbers of repeating units as polytetramethylene ether glycol are available.
  • PTMG650, PTMG850, PTMG1000, PTMG1300, PTMG1500, PTMG1800, PTMG2000 (above, manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned.
  • the molecular weight of polytetramethylene ether glycol is preferably 2000 or less.
  • R 11 in Compound C and R 12 in Compound D from the viewpoint of strong adhesion of Compound A, it is preferable that one of R 11 and R 12 is a hydrogen atom and the other is a glycidyl group.
  • the compound C and the compound D are produced by, for example, reacting the compound C and the compound D in the presence of an alkali, and then reacting the reaction product of the compound C and the compound D with the presence of an appropriate catalyst.
  • an appropriate catalyst such as epichlorohydrin.
  • the reaction described above is adjusted so that m in compound A is a number in the range of 1 to 5, preferably 1 to 4, more preferably 1 to 3, and more preferably 1 to 2.
  • the number of m can be controlled as follows when the synthesis intermediate P is synthesized in the case of the example.
  • the equivalent ratio of the compounds C1-1 and D1 is 1: 2.5.
  • this ratio is 1: 2.0 or 1: 1.5, the number of m is Increase.
  • one of R 11 in Compound C and R 12 in Compound D is a hydrogen atom, and the other is a glycidyl group.
  • the alkali is preferably an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal carbonate such as sodium carbonate or potassium carbonate from the viewpoint of rapid progress of the reaction and synthesis cost. More preferred. These alkalis are preferably used as an aqueous solution, but in some cases, a powder or solid alkali can be added simultaneously with water or separately.
  • the amount of alkali used is such that when R 11 is a hydrogen atom and R 12 is a glycidyl group from the viewpoint of rapid progress of the reaction and synthesis cost, the alkali may be equal to or more than the equivalent of the hydroxyl group, and R 11 is glycidyl.
  • R 12 is a hydrogen atom
  • a catalytic amount is sufficient, and it is 0.0001 to 0.1 equivalent, more preferably 0.0001 to 0.01 equivalent of the hydroxyl group of compound D.
  • the amount of alkali used is 0.0003 equivalent to 1 equivalent of hydroxyl group.
  • the amount of the compound such as epichlorohydrin used is preferably 0.5 to 20 equivalents, more preferably 0.5 to 15 equivalents, from the viewpoint of rapid progress of the reaction and synthesis cost.
  • Catalysts include tertiary amines such as trimethylamine, trioctylamine and tridecylamine, tetramethylammonium, methyltrioctylammonium, methyltridecylammonium and benzyltrimethylammonium from the viewpoints of reaction time, catalyst cost and catalytic activity.
  • a quaternary ammonium salt such as tetramethylammonium chloride, methyltrioctoctylammonium chloride, methyltridecylammonium chloride, and benzyltrimethylammonium chloride is preferred, and a quaternary ammonium salt is more preferred.
  • the amount of the catalyst used is preferably 0.01 to 10% by weight with respect to the total amount of compounds such as Compound C, Compound D and epichlorohydrin, from the viewpoint of appropriately securing the reaction rate while suppressing side reactions. %, More preferably 0.1 to 5% by weight.
  • the reaction with the alkali is preferably performed at 50 to 250 ° C., more preferably at 70 to 200 ° C., and further preferably at 100 to 170 ° C.
  • the reaction with the compound such as epichlorohydrin is preferably The reaction is performed at 25 to 100 ° C, more preferably 30 to 80 ° C, and further preferably 40 to 60 ° C.
  • a solvent inert to the reaction such as hydrocarbon, ether or ketone can be used, but when an excessive amount of a compound such as epichlorohydrin is used, a compound such as epichlorohydrin is used as the solvent. These solvents are not essential.
  • Purification of compound A after completion of the reaction can be performed by a conventional method, for example, by distilling off an excess of epichlorohydrin and the like, and adding a water-insoluble solvent such as hydrocarbon as necessary,
  • the desired compound A can be obtained by removing the sodium chloride and catalyst produced by washing with water.
  • the production method of the compound A of the present invention is a compound C1 (polyalkylene ether glycol diglycidyl ether in which R 11 in the compound C is a glycidyl group; for example, polyethylene glycol Diglycidyl ether), and R 12 in compound D is a compound D1 (for example, bisphenol A) in which R 12 is a hydrogen atom, the compound C1 and the compound D1 are reacted to form the compound C1 and the compound D1.
  • step 1 for obtaining the reactant P
  • step 2 for obtaining a reactant Q in which part or all of the hydroxyl groups of the reactant P are epoxidized by epoxidizing the hydroxyl group of the reactant P.
  • step 3 compound A in which group 1 or group 2 is introduced into R can be obtained through step 3 in which reactant Q is further reacted with (meth) acrylic acid in the presence of a basic catalyst.
  • a basic catalyst used by a reaction between an epoxy resin and (meth) acrylic acid can be used from the viewpoint of improving the reaction rate, rapid progress of the reaction, and catalyst cost. It is also possible to use a polymer-supported basic catalyst in which is supported on a polymer.
  • the basic catalyst is preferably a trivalent organic phosphorus compound and / or an amine compound.
  • the basic atom of the basic catalyst is phosphorus and / or nitrogen.
  • the basic catalyst a known basic catalyst used by a reaction between an epoxy resin and (meth) acrylic acid can be used.
  • a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer can also be used.
  • the basic catalyst is preferably a trivalent organic phosphorus compound and / or an amine compound.
  • the basic atom of the basic catalyst is phosphorus and / or nitrogen.
  • trivalent organic phosphorus compounds include alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof, triphenylphosphine, tri-m-tolylphosphine, tris (2, Arylphosphines such as 6-dimethoxyphenyl) phosphine and salts thereof, phosphorous acid triesters such as triphenylphosphite, triethylphosphite and tris (nonylphenyl) phosphite and salts thereof.
  • alkylphosphines such as triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine and salts thereof
  • triphenylphosphine tri-m-tolylphosphine
  • tris (2, Arylphosphines such as 6-dimethoxyphenyl
  • amine compounds include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, trisdiethylaminomethylphenol, 1,5,7-triazabicyclo [4.
  • dec-5-ene TBD
  • 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene Me-TBD
  • 1,8-diazabicyclo DBU
  • 6-dibutylamino-1,8-diazabicyclo [5.4.0] undec-7-ene 1,5-diazabicyclo [4.3.0]
  • Examples include strongly basic amines such as non-5-ene (DBN) and 1,1,3,3-tetramethylguanidine and salts thereof. Of these, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferable.
  • the salt of the amine compound include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.
  • the polymer for supporting the basic catalyst is not particularly limited, and a polymer obtained by crosslinking polystyrene with divinylbenzene, a polymer obtained by crosslinking acrylic resin with divinylbenzene, or the like is used.
  • These polymers are the solvent (for example, methyl ethyl ketone, methyl isobutyl ketone, toluene etc.) used for reaction with the epoxy resin obtained by the manufacturing method including the process 1 or processes 1 and 2, and a raw material, a product. Is insoluble.
  • a polymer-supported basic catalyst is obtained by chemically bonding a basic catalyst to an insoluble polymer or introducing a basic catalyst into a monomer, polymerizing the monomer, and then three-dimensionally crosslinking with a crosslinking monomer such as divinylbenzene.
  • a crosslinking monomer such as divinylbenzene.
  • polymer-supported basic catalyst examples include diphenylphosphinopolystyrene, 1,5,7-triazabicyclo [4.4.0] dec-5-enepolystyrene, N, N- (diisopropyl) aminomethylpolystyrene. N- (methylpolystyrene) -4- (methylamino) pyridine and the like. These polymer-supported basic catalysts may be used alone or in combination of two or more.
  • polymer-supported basic catalyst a commercially available one may be used.
  • examples of commercially available polymer-supported basic catalysts include PS-PPh 3 (diphenylphosphinopolystyrene, manufactured by Biotage), PS-TBD (1,5,7-triazabicyclo [4.4.0] deca-5. -Enpolystyrene, manufactured by Biotage Corporation).
  • the polymer-supported basic catalyst is used in an amount of 0.5 to 5.0 milliequivalents of the polymer-supported basic catalyst with respect to 1 equivalent of epoxy of the epoxy resin obtained by the production method including Step 1 or 2. Preferably, it is 1.0 to 3.0 milliequivalent. It is preferable from the viewpoint of reaction rate, reaction time, and catalyst cost that the ratio of the polymer-supported basic catalyst is within the above range.
  • the temperature in the reaction step of the epoxy resin obtained by the production method including step 1 or steps 1 and 2 and (meth) acrylic acid is preferably 60 to 120 ° C., more preferably 80 to 120 ° C. More preferably, it is 90 to 110 ° C.
  • the reaction between the epoxy resin obtained by the production method including Step 1 or Steps 1 and 2 and (meth) acrylic acid is because the partially esterified epoxy resin obtained by this reaction is cured by active energy rays such as ultraviolet rays. It is desirable to carry out the reaction in a container that shields from ultraviolet rays.
  • the reaction between the epoxy resin obtained by the production method including Step 1 or Steps 1 and 2 and (meth) acrylic acid is a reflux solvent exhibiting good solvent properties with respect to the epoxy resin in order to prevent gas phase polymerization. Although it may be performed in the presence of the solvent, in this case, since it is necessary to remove the solvent after completion of the reaction, it is preferably performed without a solvent. Examples of the reflux solvent include acetone and methyl ethyl ketone.
  • the partially esterified epoxy resin removes the polymer-supported basic catalyst. Can be obtained.
  • a method for removing the polymer-supported basic catalyst it is preferable to use filtration or centrifugation.
  • Examples of the method for filtering the polymer-supported basic catalyst include a method of filtering the polymer-supported basic catalyst using, for example, a nylon mesh NY-10HC (manufactured by Sefar, Switzerland) having an opening of 10 ⁇ m.
  • Examples of the method of centrifuging the polymer-supported basic catalyst include a method of removing the polymer-supported basic catalyst by solid-liquid separation using a centrifuge.
  • Comparative Example 1-2 (Compound B) 340 g of bisphenol A type epoxy resin (EXA850CRP, manufactured by DIC Corporation; also used as the compound of Comparative Example 1-1), 90.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 g of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) And BHT 100 mg were mixed and stirred at 100 ° C. for 6 hours. 418g of compound B of pale yellow transparent viscous substance was obtained.
  • EXA850CRP bisphenol A type epoxy resin
  • DIC Corporation also used as the compound of Comparative Example 1-1
  • methacrylic acid manufactured by Tokyo Chemical Industry Co., Ltd.
  • triphenylphosphine manufactured by Tokyo Chemical Industry Co., Ltd.
  • BHT 100 mg were mixed and stirred at 100 ° C. for 6 hours. 418g of compound B of pale yellow transparent viscous substance was obtained.
  • Example 1-1 Compound A-1 (1) Compound C1-1 (145 g (1 equivalent / epoxy group)) and bisphenol A (Compound D1) (570 g (2.5 equivalents)) are placed in an eggplant type flask so that the liquid temperature becomes 150 ° C. Stir with heating. 4 g NaOH aqueous solution 1.5g was added, and it stirred at 150 degreeC for 2 hours. The solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water.
  • Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration and the like, and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, which is a synthetic intermediate as a yellow viscous product 290 g of reaction product P-1 was obtained.
  • reaction product Q-1 pale yellow viscous compound A-1 (reaction product Q-1).
  • Example 1-2 Compound A-2
  • Compound C1-2 230 g (1 equivalent / epoxy group)
  • bisphenol A Compound D1
  • 4 g NaOH aqueous solution 1.5g was added, and it stirred at 150 degreeC for 2 hours.
  • the solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water.
  • Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is filtered off. 366 g of reaction product P-2 was obtained.
  • reaction product Q-2 The reaction mixture was cooled to room temperature, 1 L of chloroform was added, and the mixture was washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 241 g of pale yellow viscous compound A-2 (reaction product Q-2).
  • Example 1-3 (Compound A-3)
  • Denasel EX-830 (compound C1-3) (268 g (1 equivalent / epoxy group)) and bisphenol A (compound D1) (570 g (2.5 equivalents)) manufactured by Nagase ChemteX Corporation in an eggplant type flask
  • the mixture was heated and stirred so that the liquid temperature became 150 ° C. 4 g NaOH aqueous solution 1.5g was added, and it stirred at 150 degreeC for 2 hours.
  • the solution was cooled to a temperature of 60 ° C. or lower, added with 500 mL of chloroform, washed 6 times with 1 L of 1% NaOH aqueous solution and 3 times with 1 L of water.
  • Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration and the like, and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, which is a synthetic intermediate as a yellow viscous product 375 g of reaction product P-3 was obtained.
  • reaction product Q-3 pale yellow viscous compound A-3
  • Magnesium sulfate is added to the obtained organic phase, and after drying, the solid content is separated by filtration and the like, and the solvent of the obtained organic phase is distilled off by distillation under reduced pressure, which is a synthetic intermediate as a yellow viscous product 154 g of reactant P-4 was obtained.
  • reaction product Q-4 pale yellow viscous compound A-4 (reaction product Q-4).
  • Example 1-5 Compound A-5
  • a mixture of 320 g of compound A-3 (reactant Q-3), 43.05 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.25 g of triphenylphosphine (basic catalyst, produced by Tokyo Chemical Industry Co., Ltd.), and 50 mg of BHT was mixed at 100 ° C. For 8 hours. 357 g of light yellow viscous compound A-5 was obtained.
  • Examples 2-1 to 9 and Comparative Example 2-1 Each of Compound A-1 to 5 (Examples 1-1 to 5) and Compound B (Comparative Example 1-2), EY Resin KR-2 (manufactured by QSM), Zefaak F351 (manufactured by Gantz Kasei), Seahoster KE-C50HG (manufactured by Nippon Shokubai Co., Ltd.), KBM-403 (silane coupling agent: manufactured by Shin-Etsu Chemical Co., Ltd.), and Amicure VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin, Ajinomoto Fine Techno Were mixed in the blending amounts (parts by weight) shown in Table 1, and then sufficiently kneaded using a three-roll mill (C-43 / 4 ⁇ 10 manufactured by Inoue Seisakusho). Examples 2-1 to 9-9 The liquid crystal sealant of Comparative Example 2-1 was obtained
  • Viscosity measurement The viscosity was measured at 25 ° C. using an E-type viscometer (RE105U manufactured by Toki Sangyo Co., Ltd.). The rotor and the number of rotations were selected as follows. Compound A-1: 3 ° ⁇ R7.7 rotor, 5 rpm Compound A-2: 3 ° ⁇ R7.7 rotor, rotation speed 10 rpm Compound A-3: 3 ° ⁇ R14 rotor, rotation speed 5 rpm Compound A-4: 3 ° ⁇ R14 rotor, rotation speed 20 rpm Compound A-5: 3 ° ⁇ R7.7 rotor, 5 rpm EPICLON850CRP: 3 ° x R14 rotor, rotation speed 20rpm Compound B: 3 ° ⁇ R7.7 rotor, rotation speed 10 rpm
  • the NI point is measured using a differential scanning calorimeter (DSC, manufactured by PerkinElmer, Inc., PYRIS6), 10 mg of a liquid crystal sample for evaluation is enclosed in an aluminum sample pan, and the measurement is performed at a temperature rising rate of 5 ° C./min. went. In addition, 10 mg of the liquid crystal was sealed in an aluminum sample pan, and a measurement was performed under a temperature rising rate of 5 ° C./min.
  • DSC differential scanning calorimeter
  • the difference TE-TB between the blank endothermic peak top (phase transition temperature) TB and the endothermic peak top (phase transition temperature) TE of the liquid crystal for evaluation was defined as the NI point change.
  • the NI point change is as small as possible.
  • the rubbing process was performed as follows. Alignment liquid Sunever SE-7492 (Nissan Chemical Co., Ltd.) was added dropwise (0.3 MPa, 5.3 sec) to an TN6070 base (ITP base manufactured by FPD Solutions) and dried using pure water. A coater reached 5000 rpm in 10 seconds, and was applied uniformly under the condition of keeping for 20 seconds (conditions in which the orientation film thickness was 7000 to 8000 mm). After application, pre-baking (85 ° C., 1 min) on a hot plate and post-baking (230 ° C., 60 min) in an oven were performed.
  • the substrate was fed at a rotation speed of 500 rpm at a speed of 600 mm / min, and a rubbing treatment was performed with an indentation amount of 0.4 mm.
  • the rubbing direction was defined so that the facing substrate was a twist (cross) of 90 °.
  • the rubbed substrate was immersed in pure water and subjected to ultrasonic cleaning.
  • the glass substrate was dried in an oven at 120 ° C. to obtain a rubbed ITO glass substrate with an alignment film.
  • sticker point application part
  • the confirmation was performed with an optical microscope, and the polarizing plate was observed in a crossed Nicol state with a test cell sandwiched between them, and the liquid crystal (hereinafter, blank liquid crystal) in the middle part of the seal and the seal was compared with the liquid crystal state at the time of sealing.
  • a non-uniform part that is different from the state of the blank liquid crystal found when sealing If it is not observed at the time of sealing, or if it is a part of the sealing and less than 50 ⁇ m from the sealing, The case where it is a part at the time of sealing and 50 ⁇ m or more from the time of sealing, or the whole circumference at the time of sealing and less than 50 ⁇ m from the time of sealing is evaluated as ⁇ , The case of 50 ⁇ m or more from the whole circumference at the time of sealing and from the time of sealing was evaluated as x. In addition, it is thought that said non-uniform
  • FIGS. 1 and 2 show the alignment state of the liquid crystal during sealing of compounds A-3 (FIG. 1) and A-5 (FIG. 2). When it is not observed at all, it is a part at the time of sealing and less than 50 ⁇ m ( ⁇ ) from the time of sealing.
  • FIG. 3 shows the alignment state of the liquid crystal when the compound B is sealed, and the non-uniform portion different from the blank liquid crystal state found at the time of sealing is 50 ⁇ m or more ( ⁇ ) over the entire periphery of the sealing and from the sealing time. It is.
  • FIG. 4 shows an outline of the test method.
  • Each of the liquid crystal sealants of Examples 2-1 to 9 and Comparative Examples 2-1 to 3 is 15 mm ⁇ 3 mm, 15 mm ⁇ 21 mm on an ITO glass substrate (30 mm ⁇ 30 mm ⁇ 0.5 mmt) dispersed with a 6 ⁇ m spacer. Spot coating was performed so that the diameter of the liquid crystal sealant after bonding to the position was 1.5 to 2.5 mm ⁇ .
  • a glass substrate (23 mm ⁇ 23 mm ⁇ 0.5 mmt) was bonded, and ultraviolet rays (UV irradiation device: UVX-01224S1, manufactured by USHIO INC., 30 seconds at 100 mW / cm 2/365 nm) were irradiated at an illuminance of 3000 mJ / cm 2.
  • UV irradiation device UVX-01224S1, manufactured by USHIO INC., 30 seconds at 100 mW / cm 2/365 nm
  • heat curing was performed in a hot air oven at 120 ° C. for 1 hour to prepare a test piece for evaluating the adhesive strength.
  • the glass substrate of the test piece was fixed, the ITO glass substrate 15 mm ⁇ 25 mm was punched out at a speed of 5 mm / min, and the adhesive strength was evaluated.
  • Table 1 The evaluation results are shown in Table 1.
PCT/JP2013/077036 2012-10-12 2013-10-04 グリシジルエーテル系化合物、液晶シール剤及びグリシジルエーテル系化合物の製造方法 WO2014057871A1 (ja)

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WO2022270462A1 (ja) * 2021-06-22 2022-12-29 積水化学工業株式会社 液晶表示素子用シール剤及び液晶表示素子

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JP6601634B2 (ja) * 2017-03-31 2019-11-06 協立化学産業株式会社 変性樹脂及びそれを含む硬化性樹脂組成物
JP7148332B2 (ja) 2018-09-07 2022-10-05 積水化学工業株式会社 液晶表示素子用シール剤、上下導通材料、及び、液晶表示素子

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JP7253118B1 (ja) * 2021-06-22 2023-04-05 積水化学工業株式会社 液晶表示素子用シール剤及び液晶表示素子

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